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Number of published records (latest version only): 836

Number of published records (all versions): 1028

Solvation free energies from machine learning molecular dynamics


Nicephore Bonnet, Nicola Marzari

  • In this paper, we propose an extension to the approach of [Xi, C; et al. J. Chem. Theory Comput. 2022, 18, 6878] to calculate ion solvation free energies from first-principles (FP) molecular dynamics (MD) simulations of a hybrid solvation model. The approach is first re-expressed within the quasi-chemical theory of solvation. Then, to allow for longer simulation times than the original first-principles molecular dynamics approach and thus improve the convergence of statistical averages at a fraction of the original computational cost, a machine-learned (ML) energy function is trained on FP energies and forces and used in the MD simulations. The ML workflow and MD simulation times (≈200 ps) are adjusted to converge the predicted solvation energies within a chemical accuracy of 0.04 eV. The extension is successfully benchmarked on the same set of alkaline and alkaline-earth ions. The record includes all molecular-dynamics trajectories, energies and forces used to obtain the ...

Latest version: v1
Publication date: May 27, 2024

Tailoring magnetism of graphene nanoflakes via tip-controlled dehydrogenation


Chenxiao Zhao, Qiang Huang, Leoš Valenta, Kristjan Eimre, Lin Yang, Aliaksandr V. Yakutovich, Wangwei Xu, Xinliang Feng, Michal Juríček, Roman Fasel, Pascal Ruffieux, Carlo A. Pignedoli

  • Atomically precise graphene nanoflakes called nanographenes have emerged as a promising platform to realize carbon magnetism. Their ground state spin configuration can be anticipated by Ovchinnikov-Lieb rules based on the mismatch of π electrons from two sublattices. While rational geometrical design achieves specific spin configurations, further direct control over the π electrons offers a desirable extension for efficient spin manipulations and potential quantum device operations. To this end, in a recent publication, we applied a site-specific dehydrogenation using a scanning tunneling microscope tip to nanographenes deposited on a Au(111) substrate, which showed the capability of precisely tailoring the underlying π-electron system and therefore efficiently manipulating their magnetism. Through first-principles calculations and tight-binding meanfield-Hubbard modeling, we demonstrated that the dehydrogenation-induced Au—C bond formation along with the resulting hybridization ...

Latest version: v1
Publication date: May 23, 2024

Emergent half-metal with mixed structural order in (111)-oriented (LaMnO₃)₂ₙ|(SrMnO₃)ₙ superlattices


Fabrizio Cossu, Jùlio Alves Do Nascimento, Stuart A. Cavill, Igor Di Marco, Vlado K. Lazarov, Heung-Sik Kim

  • Using first-principles techniques, we study the structural, magnetic, and electronic properties of (111)-oriented (LaMnO₃)₂ₙ|(SrMnO₃)ₙ superlattices of varying thickness (n=2,4,6). We find that the properties of the thinnest superlattice (n=2) are similar to the celebrated half-metallic ferromagnetic alloy La2/3Sr1/3⁢MnO₃, with quenched Jahn-Teller distortions. At intermediate thickness (n=4), the a⁻a⁻a⁻ tilting pattern transitions to the a⁻a⁻c⁺ tilting pattern, driven by the lattice degrees of freedom in the LaMnO₃ region. The emergence of the Jahn-Teller modes and the spatial extent needed for their development play a key role in this structural transition. For the largest thickness considered (n=6), we unveil an emergent separation of Jahn-Teller and volume-breathing orders in the ground-state structure with the a⁻a⁻c⁺ tilting pattern, whereas it vanishes in the antiferromagnetic configurations. The ground state of all superlattices is half-metallic ...

Latest version: v1
Publication date: May 23, 2024

Unearthing the foundational role of anharmonicity in heat transport in glasses


Alfredo Fiorentino, Enrico Drigo, Stefano Baroni, Paolo Pegolo

  • The time-honored Allen-Feldman theory of heat transport in glasses is generally assumed to predict a finite value for the thermal conductivity, even if it neglects the anharmonic broadening of vibrational normal modes. We demonstrate that the harmonic approximation predicts that the bulk lattice thermal conductivity of harmonic solids inevitably diverges at any temperature, irrespective of configurational disorder, and that its ability to represent the heat-transport properties observed experimentally in most glasses is implicitly due to finite-size effects. Our theoretical analysis is thoroughly benchmarked against careful numerical simulations. Our findings thus reveal that a proper account of anharmonic effects is indispensable to predict a finite value for the bulk thermal conductivity in any solid material, be it crystalline or glassy. This record contains data and scripts to support the findings of the manuscript and ensure their reproducibility.

Latest version: v1
Publication date: May 23, 2024

The energy landscape of magnetic materials


Louis Ponet, Enrico Di Lucente, Nicola Marzari

  • Magnetic materials can display many solutions to the electronic-structure problem, corresponding to different local or global minima of the energy functional. In Hartree-Fock or density-functional theory different single-determinant solutions lead to different magnetizations, ionic oxidation states, hybridizations, and inter-site magnetic couplings. The vast majority of these states can be fingerprinted through their projection on the atomic orbitals of the magnetic ions. We have devised an approach that provides an effective control over these occupation matrices, allowing us to systematically explore the landscape of the potential energy surface. We showcase the emergence of a complex zoology of self-consistent states; even more so when semi-local density-functional theory is augmented - and typically made more accurate - by Hubbard corrections. Such extensive explorations allow to robustly identify the ground state of magnetic systems, and to assess the accuracy (or not) of current functionals and approximations

Latest version: v1
Publication date: May 23, 2024

Dramatic acceleration of the Hopf cyclization on gold(111): from enediynes to unusual graphene nanoribbons


Chenxiao Zhao, Carlo A. Pignedoli, Dayanni D. Bhagwandin, Wangwei Xu, Pascal Rufieux, Roman Fasel, Yves Rubin

  • Hopf et al. first reported the high-temperature 6π-electrocyclization of cis-hexa-1,3-diene-5-yne to benzene in 1969. Subsequent studies using this cyclization have been limited by its very high reaction barrier. Here, we show that the reaction barrier for two model systems, (E)-1,3,4,6-tetraphenyl-3-hexen-1,5-diyne (1a) and (E)-3,4-bis(4-iodophenyl)-1,6-diphenyl-3-hexen-1,5-diyne 1b, is decreased by nearly half on a Au(111) surface. In recent work, we have used scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM) to monitor the Hopf cyclization of enediynes 1a,b on Au(111). Enediyne 1a undergoes two sequential, quantitative Hopf cyclizations, first to naphthalene derivative 2, and finally to chrysene 3. Density functional theory (DFT) calculations reveal that a gold atom from the Au(111) surface is involved in all steps of this reaction, and that it is crucial to lowering the reaction barrier. Our findings have important implications for the ...

Latest version: v1
Publication date: May 21, 2024

Electronic decoupling and hole-doping of graphene nanoribbons on metal substrates by chloride intercalation


Amogh Kinikar, Thorsten G. Englmann, Marco Di Giovannantonio, Nicolò Bassi, Feifei Xiang, Samuel Stolz, Roland Widmer, Gabriela Borin Barin, Elia Turco, Néstor Merino Díez, Kristjan Eimre, Andres Ortega-Guerrero, Xinliang Feng, Oliver Gröning, Carlo Antonio Pignedoli, Roman Fasel, Pascal Ruffieux

  • In this record we provide the data to support our recent finding on the intercalation of gold chloride underneath atomically precise graphene nanoribbons (GNRs). GNRs have a wide range of electronic properties that depend sensitively on their chemical structure. Several types of GNRs have been synthesized on metal surfaces through selective surface-catalyzed reactions. The resulting GNRs are adsorbed on the metal surface, which may lead to hybridization between the GNR orbitals and those of the substrate. This makes investigation of the intrinsic electronic properties of GNRs more difficult, and also rules out capacitive gating. In the manuscript where the data presented here is discussed, we demonstrate the formation of a dielectric gold chloride adlayer that can intercalate underneath GNRs on the Au(111) surface. The intercalated gold chloride adlayer electronically decouples the GNRs from the metal and leads to a substantial hole doping of the GNRs. Our results introduce an ...

Latest version: v1
Publication date: May 16, 2024

FINALES - Electrolyte optimization for maximum conductivity and for maximum cycle life


Simon K. Steensen, Monika Vogler, Francisco Fernando Ramirez, Leon Merker, Jonas Busk, Johan M. Carlsson, Laura Hannemose Rieger, Bojing Zhang, Francois Liot, Giovanni Pizzi, Felix Hanke, Eibar Flores, Hamidreza Hajiyani, Stefan Fuchs, Alexey Sanin, Miran Gaberšček, Ivano E. Castelli, Simon Clark, Tejs Vegge, Arghya Bhowmik, Helge S. Stein

  • This study investigates an electrolyte system composed of lithium hexafluorophosphate (LiPF6), ethylene carbonate (EC) and ethyl methyl carbonate (EMC). For the assembly of full cells, electrodes based on graphite and lithium nickel dioxide (LNO) are used. This work provides insight into the similarity of formulations of an electrolyte optimized for maximum conductivity and another one optimized for maximum cycle life are expected to be in this chemical system. The goal is to assess whether it is promising to target research efforts on finding an electrolyte formulation within this chemical space which can fulfill both requirements. A campaign utilizing the latest version of FINALES is designed to determine conductivity values and predict end of life for various electrolyte formulations containing the aforementioned chemicals. The campaigns were able to reproducibly identify regions of high ionic conductivity of the aforementioned chemical composition. The ML methodology applied ...

Latest version: v1
Publication date: May 14, 2024

First-principles thermodynamics of precipitation in aluminum-containing refractory alloys


Yann Lorris Müller, Anirudh Raju Natarajan

  • Materials for high-temperature environments are actively being investigated for deployment in aerospace and nuclear applications. This study uses computational approaches to unravel the crystallography, and thermodynamics of a promising class of refractory alloys containing aluminum. Accurate first-principles calculations, cluster expansion models, and statistical mechanics techniques are employed to rigorously analyze precipitation in a prototypical senary Al-Nb-Ta-Ti-V-Zr alloy. Finite-temperature calculations reveal a strong tendency for aluminum to segregate to a single sublattice at elevated temperatures. Precipitate and matrix compositions computed with our ab-initio model are in excellent agreement with previous experimental measurements (Soni et al., 2020). Surprisingly, conventional B2-like orderings are found to be both thermodynamically and mechanically unstable in this alloy system. Complex anti-site defects are essential to forming a stable ordered precipitate. Our ...

Latest version: v1
Publication date: May 14, 2024

Seebeck coefficient of ionic conductors from Bayesian regression analysis


Enrico Drigo, Stefano Baroni, Paolo Pegolo

  • We propose a novel approach to evaluating the ionic Seebeck coefficient in electrolytes from relatively short equilibrium molecular dynamics simulations, based on the Green-Kubo theory of linear response and Bayesian regression analysis. By exploiting the probability distribution of the off-diagonal elements of a Wishart matrix, we develop a consistent and unbiased estimator for the Seebeck coefficient, whose statistical uncertainty can be arbitrarily reduced in the long-time limit. We assess the efficacy of our method by benchmarking it against extensive equilibrium molecular dynamics simulations conducted on molten CsF using empirical force fields. We then employ this procedure to calculate the Seebeck coefficient of molten NaCl, KCl and LiCl using neural network force fields trained on ab initio data over a range of pressure-temperature conditions.

Latest version: v1
Publication date: May 13, 2024

Ferrimagnetism induced by thermal vibrations in oxygen-deficient manganite heterostructures


Moloud Kaviani, Chiara Ricca, Ulrich Aschauer

  • Super-exchange most often leads to antiferromagnetism in transition-metal perovskite oxides, yet ferromagnetism or ferrimagnetism would be preferred for many applications, for example in data storage. While alloying, epitaxial strain and defects were shown to lead to ferromagnetism, engineering this magnetic order remains a challenge. We propose, based on density functional theory calculations, a novel route to defect-engineer ferrimagnetism, which is based on preferential displacements of oxygen vacancies due to finite temperature vibrations. This mechanism has an unusual temperature dependence, as it is absent at 0K, strengthens with increasing temperature before vanishing once oxygen vacancies disorder, giving it a unique experimentally detectable signature.

Latest version: v1
Publication date: May 13, 2024

Reduction of precious metal ions in aqueous solutions by contact-electro-catalysis


Yusen Su, Andy Berbille, Xiao-Fen Li, Jinyang Zhang, MohammadJavad PourhosseiniAsl, Huifan Li, Zhanqi Liu, Shunning Li, Jian-Bo Liu, Laipan Zhu, Zhong Lin Wang

  • Contact-Electro-Catalysis is an emerging catalytic principle that takes advantage of exchanges of electrons occurring through contact electrification events at solid-liquid interfaces to initiate or drive the catalysis of redox reactions. In this publication, the authors have proven the ability of various polymer insulators to catalyze the reduction of a wide variety of metal ions in aqueous solution, in both aerobic and anaerobic conditions. This property of the dielectric polymers was employed to design a 1-step method to selectively extract gold from e-waste leachates. In anaerobic conditions, the rate of the reactions increase due to the absence of competition form oxygen for the electrons. The influence of metal ions in solution on the distance between O₂ and the polymer chain of polytetrafluoroethylene was evaluated, as well as the resulting adsorption energy. The effect of tacticity on the ability of polymers such as PP to perform the contact-electro-catalytic reduction of ...

Latest version: v1
Publication date: May 08, 2024

Neural network potential for Zr-H


Manura Liyanage, David Reith, Volker Eyert, W. A. Curtin

  • The introduction of Hydrogen (H) into Zirconium (Zr) influences many mechanical properties, especially due to low H solubility and easy formation of Zirconium hydride phases. Understanding the various effects of H requires studies with atomistic resolution but at scales that incorporate defects such as cracks, interfaces, and dislocations. Such studies thus demand accurate interatomic potentials. Here, a neural network potential (NNP) for the Zr-H system is developed within the Behler-Parrinello framework. The Zr-H NNP retains the accuracy of a recent NNP for hcp Zr and exhibits excellent agreement with first-principles density functional theory (DFT) for (i) H interstitials and their diffusion in hcp Zr, (ii) formation energies, elastic constants, and surface energies of relevant Zr hydrides, and (iii) energetics of a common Zr/Zr-H interface. The Zr-H NNP shows physical behavior for many different crack orientations in the most-stable ε-hydride and structures and reasonable ...

Latest version: v1
Publication date: May 03, 2024

Achieving 19% efficiency in nonfused ring electron acceptor solar cells via solubility control of donor and acceptor crystallisation


Rui Zeng, Ming Zhang, Xiaodong Wang, Lei Zhu, Bonan Hao, Wenkai Zhong, Guanqing Zhou, Jiawei Deng, Senke Tan, Jiaxing Zhuang, Fei Han, Anyang Zhang, Zichun Zhou, Xiaonan Xue, Shengjie Xu, Jinqiu Xu, Yahui Liu, Hao Lu, Xuefei Wu, Cheng Wang, Zachary Fink, Thomas P. Russell, Hao Jing, Yongming Zhang, Zhishan Bo, Feng Liu

  • Nonfused ring electron acceptors (NFREAs) are interesting n-type near infrared (NIR) photoactive semiconductors with strong molecular absorption and easy synthetic route. However, the low backbone planarity and bulky substitution make NFREA less crystalline, which significantly retards charge transport and the formation of bicontinuous morphology in organic photovoltaic device. Donor and acceptor solubility in different solvents is studied, and the created solubility hysteresis can induce the formation of the highly crystalline donor polymer fibril to purify the NFREA phase, thus a better bicontinuous morphology with improved crystallinity. Based on these results, a general solubility hysteresis sequential condensation (SHSC) thin film fabrication methodology is established to produce highly uniform and smooth photoactive layer. The well-defined interpenetrating network morphology afforded a record efficiency of 19.02%, which is ~22% improvement comparing to conventional device ...

Latest version: v2
Publication date: Apr 29, 2024

A general framework for active space embedding methods: applications in quantum computing


Stefano Battaglia, Max Rossmannek, Vladimir V. Rybkin, Ivano Tavernelli, Juerg Hutter

  • We developed a general framework for hybrid quantum-classical computing of molecular and periodic embedding calculations based on an orbital space separation of the fragment and environment degrees of freedom. We show its potential by presenting a specific implementation of periodic range-separated DFT coupled to a quantum circuit ansatz, whereby the variational quantum eigensolver and the quantum equation-of-motion approach are used to obtain the low-lying spectrum of the embedded fragment Hamiltonian. Application of this scheme to study strongly correlated molecular systems and localized electronic states in materials is showcased through the accurate prediction of the optical properties for the neutral oxygen vacancy in magnesium oxide (MgO). Despite some discrepancies in absorption predictions, the method demonstrates competitive performance with state-of-the-art ab initio approaches, particularly evidenced by the accurate prediction of the photoluminescence emission peak.

Latest version: v1
Publication date: Apr 26, 2024

High-throughput computational screening for solid-state Li-ion conductors


Leonid Kahle, Aris Marcolongo, Nicola Marzari

  • We present a computational screening of experimental structural repositories for fast Li-ion conductors, with the goal of finding new candidate materials for application as solid-state electrolytes in next-generation batteries. We start from ~1400 unique Li-containing materials, of which ~900 are insulators at the level of density-functional theory. For those, we calculate the diffusion coefficient in a highly automated fashion, using extensive molecular dynamics simulations on a potential energy surface (the recently published pinball model) fitted on first-principles forces. The ~130 most promising candidates are studied with full first-principles molecular dynamics, first at high temperature and then more extensively for the 78 most promising candidates. The results of the first-principles simulations of the candidate solid-state electrolytes found are discussed in detail. Update April 2024: Files are added that facilitate the Materials Cloud Archive OPTIMADE service to serve ...

Latest version: v2
Publication date: Apr 26, 2024

High-throughput dataset of impurity adsorption on common catalysts in biomass upgrading applications


Michelle A. Nolen, Sean A. Tacey, Martha A. Arellano-Treviño, Kurt M. Van Allsburg, Carrie A. Farberow

  • An extensive dataset consisting of adsorption energies of pernicious impurities present in biomass upgrading processes on common catalysts and support materials has been generated. This work aims to inform catalyst and process development for the conversion of biomass-derived feedstocks to fuels and chemicals. A high-throughput workflow was developed to execute density functional theory calculations for a diverse set of atomic (Al, B, Ca, Cl, Fe, K, Mg, Mn, N, Na, P, S, Si, Zn) and molecular (COS, H₂S, HCl, HCN, K₂O, KCl, NH₃) species on 35 unique surfaces for transition-metal (Ag, Au, Co, Cu, Fe, Ir, Ni, Pd, Pt, Re, Rh, Ru) and metal-oxide (Al₂O₃, MgO, anatase-TiO₂, rutile-TiO₂, ZnO, ZrO₂) catalysts and supports. Approximately 3,000 unique adsorption geometries were obtained. The data record includes structure and calculation output files for each unique adsorbate geometry on each surface.

Latest version: v1
Publication date: Apr 26, 2024

Dataset of disorder-stabilized unfavorable coordination in complex ABX₂ compounds


Han-Pu Liang, Chuan-Nan Li, Ran Zhou, Xun Xu, Xie Zhang, Jingxiu Yang, Su-Huai Wei

  • The crystal structure of a material is essentially determined by the nature of its chemical bonding. Consequently, the atomic coordination intimately correlates with the degree of ionicity or covalency of the material. Based on this principle, materials with similar chemical compositions can be successfully categorized into different coordination groups. However, counterexamples recently emerged in complex ternary compounds. For instance, strongly covalent IB-IIIA-VIA₂ compounds, such as AgInS₂, prefer tetrahedrally coordinated structure (TCS), while strongly ionic IA-VA-VIA₂ compounds, such as NaBiS₂, would favor octahedrally coordinated structure (OCS). One naturally expects that IB-VA-VIA₂ compounds with intermediate ionicity or covalency, such as AgBiS₂, should then have a mix-coordinated structure (MCS) consisting of covalent AgS₄ tetrahedra and ionic BiS₆ octahedra. Surprisingly, only OCS was observed experimentally for AgBiS₂. To resolve this puzzle, we perform ...

Latest version: v1
Publication date: Apr 24, 2024

"Fraternal-twin” ferroelectricity: competing polar states in hydrogen-doped samarium nickelate from first principles


Michele Kotiuga, Karin M. Rabe

  • This work explores hydrogen-doped samarium nickelate from first-principles calculations. At a concentration of 1/4 hydrogen per formula unit we find a number of polar states due to the presence of the interstitial hydrogen. Physically, the polarization of the material arises from the localization of the hydrogen's valence electron on a nearby nickel-oxygen octahedron leading to a local dipole. Due to the inherent tilt pattern present in samarium nickelate, a perovskite with an a-a-c+ tilt pattern, there is an insurmountable energy barrier to switch a given polar state the structure related by inversion symmetry. Instead, we use an in-plane epitaxial constraint to tune the total energy of two structures to be equal. These two structures, unrelated by a cell-symmetry operation, have similar a similar position of the interstitial hydrogen atom, but the valence electron localizes on a different nickel-oxygen octahedron leading to different polarizations. We find that there is a ...

Latest version: v1
Publication date: Apr 23, 2024

High-quality data enabling universality of band-gap descriptor and discovery of photovoltaic perovskites


Haiyuan Wang, Runhai Ouyang, Wei Chen, Alfredo Pasquarello

  • Extensive machine-learning assisted research has been dedicated to predicting band gaps for perovskites, driven by their immense potential in photovoltaics. Yet, the effectiveness is often hampered by the lack of high-quality band-gap datasets, particularly for perovskites involving d orbitals. In this work, we consistently calculate a large dataset of band gaps with a high level of accuracy, which is rigorously validated by experimental and state-of-the-art GW band gaps. Leveraging this achievement, our machine-learning derived descriptor exhibits exceptional universality and robustness, proving effectiveness not only for single and double, halide and oxide perovskites regardless of the underlying atomic structures, but also for hybrid organic-inorganic perovskites. With this approach, we comprehensively explore up to 15,659 materials, unveiling 14 unreported lead-free perovskites with suitable band gaps for photovoltaics. Notably, MASnBr₃, FA₂SnGeBr₆, MA₂AuAuBr₆, FA₂AuAuBr₆, ...

Latest version: v1
Publication date: Apr 23, 2024

Trimmed graphene nanoribbon junctions dataset


Julien Leuenberger, Kristiāns Čerņevičs, Oleg V. Yazyev

  • As Moore's law approaches its fundamental limits, the development of nanoelectronic devices using low-dimension materials has become a promising avenue for further miniaturization and performance improvements. Among the various novel materials, graphene nanoribbons (GNRs) have emerged as particularly attractive candidates due to their unique electronic properties, opening up a whole new nanoelectronics paradigm consisting of circuits made entirely of graphene. However, due to the technical constraints that naturally arise when working on a two-dimensional plane, the design of efficient nanoelectronic components with a minimal spatial footprint remains a significant challenge. This dataset provides a comprehensive dataset of over 1'500 armchair GNR junctions or various sizes and shapes.

Latest version: v1
Publication date: Apr 18, 2024

A FEM dataset of Ge film profiles and elastic energies for machine learning approximation of strain state and morphological evolution


Daniele Lanzoni, Fabrizio Rovaris, Luis Martín-Encinar, Andrea Fantasia, Roberto Bergamaschini, Francesco Montalenti

  • Machine Learning (ML) can be conveniently applied to continuum materials simulations, allowing for the investigation of larger systems and longer timescales, pushing the limits of tractable systems. Here we provide a comprehensive dataset of strained Ge films on Si and their corresponding strain states, which can be used to train a ML model capable of such acceleration. Approximately 80k 2D cases are included, reporting the profiles h(x) and the corresponding elastic energy densities and strain fields. The profiles are conveniently sampled using Perlin-noise and pure-sine waves. A 100nm-large computational domain is considered. The mechanical equilibrium problem is solved using Finite Element Method (FEM). Ge is modeled as an isotropic material and an eigenstrain of 3.99% is used, as in Ge/Si(001). The database has been exploited for training a (fully) Convolutional Neural Network (CNN) which maps the free surface profile h(x) to the corresponding energy density. If plugged into ...

Latest version: v1
Publication date: Apr 18, 2024

Engineering frustrated lewis pair active sites in porous organic scaffolds for catalytic CO₂ hydrogenation


Shubhajit Das, Ruben Laplaza, J. Terence Blaskovits, Clemence Corminboeuf

  • Frustrated Lewis pairs (FLPs), featuring reactive combinations of Lewis acids and Lewis bases, have been utilized for myriad metal-free homogeneous catalytic processes. Immobilizing the active Lewis sites to a solid support, especially to porous scaffolds, has shown great potential to ameliorate FLP catalysis by circumventing some of its inherent drawbacks, such as product separation and catalyst recyclability. Nevertheless, designing immobilized Lewis pair active sites (LPASs) is challenging due to the requirement of placing the donor and acceptor centers in appropriate geometric arrangements while maintaining the necessary chemical environment to perform catalysis, and clear design rules have not yet been established. In this work, we formulate simple guidelines to build highly active LPASs for direct catalytic hydrogenation of CO₂ through a large-scale screening of a diverse library of 25,000 immobilized FLPs. The library is built by introducing boron-containing acidic sites ...

Latest version: v3
Publication date: Apr 17, 2024

Thermal transport of Li₃PS₄ solid electrolytes with ab initio accuracy


Davide Tisi, Federico Grasselli, Lorenzo Gigli, Michele Ceriotti

  • The vast amount of computational studies on electrical conduction in solid-state electrolytes is not mirrored by comparable efforts addressing thermal conduction, which has been scarcely investigated despite its relevance to thermal management and (over)heating of batteries. The reason for this lies in the complexity of the calculations: on one hand, the diffusion of ionic charge carriers makes lattice methods formally unsuitable due to the lack of equilibrium atomic positions needed for normal-mode expansion. On the other hand, the prohibitive cost of large-scale molecular dynamics (MD) simulations of heat transport in large systems at ab initio levels has hindered the use of MD-based methods. In this work, we leverage recently developed machine-learning potentials targeting different ab initio functionals (PBEsol, r2SCAN, PBE0) and a state-of-the-art formulation of the Green-Kubo theory of heat transport in multicomponent systems to compute the thermal conductivity of a ...

Latest version: v1
Publication date: Apr 16, 2024

Phononic origin of the infrared dielectric properties of RE₂O₃ (RE = Y, Gd, Ho, Lu) compounds


Yixiu Luo, Juan Wang, Luchao Sun, Jingyang Wang

  • Understanding the phononic origin of the infrared dielectric properties of yttria (Y₂O₃) and other rare-earth sesquioxides (RE₂O₃) is a fundamental task in the search of appropriate RE₂O₃ materials that serve particular infrared optical applications. We herein investigate the infrared dielectric properties of RE₂O₃ (RE = Y, Gd, Ho, Lu) using DFT-based phonon calculations and Lorentz oscillator model. The abundant IR-active optical phonon modes that are available for effective absorption of photons result in high reflectance of RE₂O₃, among which four IR-active modes originated from large distortions of REO₆ octahedra are found to contribute dominantly to the phonon dielectric constants. Particularly, the present calculation method by considering one-phonon absorption process is demonstrated with good reliability in predicting the infrared dielectric parameters of RE₂O₃ at the far-infrared as well as the vicinity of mid-infrared region, and the potential cutoff frequency/wavelength ...

Latest version: v1
Publication date: Apr 15, 2024

A NN-Potential for phase transformations in Ge


Andrea Fantasia, F. Rovaris, O. Abou El Kheir, A. Marzegalli, D. Lanzoni, L. Pessina, P. Xiao, C. Zhou, L. Li, G. Henkelman, E. Scalise, F. Montalenti

  • In a recent preprint, entitled: "Development of a machine learning interatomic potential for exploring pressure-dependent kinetics of phase transitions in Germanium", we presented a novel Neural-Network (NN) interatomic potential for Ge. We recall that Ge phases different from the cubic-diamond one are of particular interest for applications. Hexagonal Ge, for instance, displays superior optical properties. It is therefore important to investigate how, exploiting pressure, Ge can be transformed into different allotropes. In order to build a potential tackling kinetics of pressure-induced phase transformations, several kinetic paths (mainly sampled using the solid-state Nudged Elastic Band method) were added to the database, following a suitable active-learning procedure. Energies, forces, and stressed relative to the various configurations were computed ab initio using VASP with the PBE functional. The NN potential was trained using the Deep Potential Molecular Dynamic package ...

Latest version: v1
Publication date: Apr 11, 2024

Modeling the ferroelectric phase transition in barium titanate with DFT accuracy and converged sampling


Lorenzo Gigli, Alexander Goscinski, Michele Ceriotti, Gareth A. Tribello

  • The accurate description of the structural and thermodynamic properties of ferroelectrics has been one of the most remarkable achievements of Density Functional Theory (DFT). However, running large simulation cells with DFT is computationally demanding, while simulations of small cells are often plagued with non-physical effects that are a consequence of the system's finite size. Therefore, one is often forced to use empirical models that describe the physics of the material in terms of effective interaction terms, that are fitted using the results from DFT, to perform simulations that do not suffer from finite size effects. In this study we use a machine-learning (ML) potential trained on DFT, in combination with accelerated sampling techniques, to converge the thermodynamic properties of Barium Titanate (BTO) with first-principles accuracy and a full atomistic description. Our results indicate that the predicted Curie temperature depends strongly on the choice of DFT functional ...

Latest version: v1
Publication date: Apr 10, 2024

Orbital-resolved DFT+U for molecules and solids


Eric Macke, Iurii Timrov, Nicola Marzari, Lucio Colombi Ciacchi

  • We present an orbital-resolved extension of the Hubbard U correction to density-functional theory (DFT). Compared to the conventional shell-averaged approach, the prediction of energetic, electronic and structural properties is strongly improved, particularly for compounds characterized by both localized and hybridized states in the Hubbard manifold. The numerical values of all Hubbard parameters are readily obtained from linear-response calculations. The relevance of this more refined approach is showcased by its application to bulk solids pyrite (FeS₂) and pyrolusite (β-MnO₂), as well as to six Fe(II) molecular complexes. Our findings indicate that a careful definition of Hubbard manifolds is indispensable for extending the applicability of DFT+U beyond its current boundaries. The present orbital-resolved scheme aims to provide a computationally undemanding yet accurate tool for electronic structure calculations of charge-transfer insulators, transition-metal (TM) complexes and ...

Latest version: v1
Publication date: Apr 08, 2024

Phonon-limited mobility for electrons and holes in highly-strained silicon


Nicolas Roisin, Guillaume Brunin, Gian-Marco Rignanese, Denis Flandre, Jean-Pierre Raskin, Samuel Poncé

  • Strain engineering is a widely used technique for enhancing the mobility of charge carriers in semiconductors, but its effect is not fully understood. In this work, we perform first-principles calculations to explore the variations of the mobility of electrons and holes in silicon upon deformation by uniaxial strain up to 2% in the [100] crystal direction. We compute the π₁₁ and π₁₂ electron piezoresistances based on the low-strain change of resistivity with temperature in the range 200 K to 400 K, in excellent agreement with experiment. We also predict them for holes which were only measured at room temperature. Remarkably, for electrons in the transverse direction, we predict a minimum room-temperature mobility about 1200 cm²/Vs at 0.3% uniaxial tensile strain while we observe a monotonous increase of the longitudinal transport, reaching a value of 2200 cm²/Vs at high strain. We confirm these findings experimentally using four-point bending measurements, establishing the ...

Latest version: v3
Publication date: Apr 03, 2024

Spectroscopic investigations of complex electronic interactions by elemental doping and material compositing of cobalt oxide for enhanced oxygen evolution reaction activity


Jinzhen Huang, Adam H. Clark, Natasha Natasha Hales, Camelia Nicoleta Borca, Thomas Huthwelker, Thomas J. Schmidt, Emiliana Fabbri

  • Doping and compositing are two universal design strategies used to engineer the electronic state of a material and mitigate its disadvantages. These two strategies have been extensively applied to the design of efficient electrocatalysts for water splitting. Using cobalt oxide (CoO) as a model catalyst, we prove that the oxygen evolution reaction (OER) performance could be progressively improved, first by Fe-doping to form Fe-CoO solid solution, and further by the addition of CeO2 to produce a Fe-CoO/CeO2 composite. X-ray adsorption spectroscopy (XAS) reveals that distinct electronic interactions are induced by the processes of doping and compositing. Fe-doping of CoO can break down the structural symmetry in the pristine material, changing the electronic structure of both Co and O species at the surface and decreasing the flat-band potential (Vfb). In comparison, subsequent compositing of Fe-CoO with CeO2 induces negligible electronic changes in the as-synthesized Fe-CoO (as seen ...

Latest version: v1
Publication date: Mar 26, 2024

Automated all-functionals infrared and Raman spectra


Lorenzo Bastonero, Nicola Marzari

  • Infrared and Raman spectroscopies are ubiquitous techniques employed in many experimental laboratories, thanks to their fast and non-destructive nature able to capture materials' features as spectroscopic fingerprints. Nevertheless, these measurements frequently need theoretical support in order to unambiguously decipher and assign complex spectra. Linear-response theory provides an effective way to obtain the higher-order derivatives needed, but its applicability to modern exchange-correlation functionals remains limited. Here, we devise an automated, open-source, user-friendly approach based on ground-state density-functional theory and the electric enthalpy functional to allow seamless calculations of first-principles infrared and Raman spectra. By employing a finite-displacement and finite-field approach, we allow for the use of any functional, as well as an efficient treatment of large low-symmetry structures. Additionally, we propose a simple scheme for efficiently sampling ...

Latest version: v2
Publication date: Mar 22, 2024

Complexity of many-body interactions in transition metals via machine-learned force fields from the TM23 data set


Cameron Owen, Steven Torrisi, Yu Xie, Simon Batzner, Kyle Bystrom, Jennifer Coulter, Albert Musaelian, Lixin Sun, Boris Kozinsky

  • This work examines challenges associated with the accuracy of machine-learned force fields (MLFFs) for bulk solid and liquid phases of d-block elements. In exhaustive detail, we contrast the performance of force, energy, and stress predictions across the transition metals for two leading MLFF models: a kernel-based atomic cluster expansion method implemented using sparse Gaussian processes (FLARE), and an equivariant message-passing neural network (NequIP). Early transition metals present higher relative errors and are more difficult to learn relative to late platinum- and coinage-group elements, and this trend persists across model architectures. Trends in complexity of interatomic interactions for different metals are revealed via comparison of the performance of representations with different many-body order and angular resolution. Using arguments based on perturbation theory on the occupied and unoccupied d states near the Fermi level, we determine that the large, sharp d ...

Latest version: v1
Publication date: Mar 22, 2024

Nonempirical semilocal density functionals for correcting the self-interaction of polaronic states


Stefano Falletta, Alfredo Pasquarello

  • Through the use of the piecewise-linearity condition of the total energy, we correct the self-interaction for the study of polarons by constructing nonempirical functionals at the semilocal level of theory. We consider two functionals, the γDFT and the μDFT functionals, both of which are based on the addition of a weak local potential to the semilocal Hamiltonian to enforce the piecewise-linearity condition. We show that the resulting polaron properties are in good agreement with reference hybrid functional calculations. This supports the use of semilocal functionals for calculating polaron properties.

Latest version: v1
Publication date: Mar 19, 2024

Non-equilibrium nature of fracture determines the crack path


Pengjie Shi, Shizhe Feng, Zhiping Xu

  • A high-fidelity neural network-based force field (NN-F³) is developed to cover the space of strain states up to material failure and the non-equilibrium, intermediate nature of fracture. Simulations of fracture in 2D crystals using NN-F³ reveal spatial complexities from lattice-scale kinks to sample-scale patterns. We find that the fracture resistance cannot be captured by the energy densities of relaxed edges as used in the literature. Instead, the fracture patterns, critical stress intensity factors at the kinks, and energy densities of edges in the intermediate, unrelaxed states offer reasonable measures for the fracture toughness and its anisotropy.

Latest version: v4
Publication date: Mar 12, 2024

The initial stages of cement hydration at the molecular level


Xinhang Xu, Chongchong Qi, Xabier M. Aretxabaleta, Chundi Ma, Dino Spagnoli, Hegoi Manzano

  • Cement hydration is crucial for the strength development of cement-based materials; however, the mechanism that underlies this complex reaction remains poorly understood at the molecular level. An in-depth understanding of cement hydration is required for the development of environmentally friendly cement and consequently the reduction of carbon emissions in the cement industry. Here, we use molecular dynamics simulations with a reactive force field to investigate the initial hydration processes of tricalcium silicate (C₃S) and dicalcium silicate (C₂S) up to 40 ns. Our simulations provide theoretical support for the rapid initial hydration of C₃S compared to C₂S at the molecular level. The dissolution pathways of calcium ions in C₃S and C₂S are revealed, showing that, two dissolution processes are required for the complete dissolution of calcium ions in C₃S. Our findings promote the understanding of the calcium dissolution stage and serve as a valuable reference for the investigation of the initial cement hydration.

Latest version: v1
Publication date: Mar 11, 2024

An anisotropic lattice Boltzmann - phase field model for dendrite growth and movement in rapid solidification of binary alloys


Shilin Mao, Yuting Cao, Wei Chen, Dongke Sun

  • In this paper, we proposed a model coupling the lattice Boltzmann and the phase field methods with anisotropic effects is proposed, which is used to numerically describe the growth and movement of dendrites in rapid solidification of alloys. The model was applied to investigate the effects of dendrite movement and interfacial non-equilibrium on evolution of dendritic patterns for Si-9.0at%As and the CET for Al-3.0wt%Cu alloys. Both the growth and remelt processes of isolated dendrites are studied, and the result reveals the remelting influences on dendrite growth and solute micro-segregation in the condition of directional solidification. This dataset contains the underlying data for the above. This work demonstrates that the proposed model has a wide range of applicability and great potential to simulate the microstructure evolution with various solidification conditions.

Latest version: v1
Publication date: Mar 06, 2024

Surface segregation in high-entropy alloys from alchemical machine learning: dataset HEA25S


Arslan Mazitov, Maximilian A. Springer, Nataliya Lopanitsyna, Guillaume Fraux, Sandip De, Michele Ceriotti

  • High-entropy alloys (HEAs), containing several metallic elements in near-equimolar proportions, have long been of interest for their unique mechanical properties. More recently, they have emerged as a promising platform for the development of novel heterogeneous catalysts, because of the large design space, and the synergistic effects between their components. In this work we use a machine-learning potential that can model simultaneously up to 25 transition metals (d-block transition metals, excluding Tc, Cd, Re, Os and Hg) to study the tendency of different elements to segregate at the surface of a HEA. In this record, we provide a dataset HEA25S, containing 10000 bulk HEA structures (Dataset O), 2640 HEA surface slabs (Dataset A), together with 1000 bulk and 1000 surface slabs snapshots from the molecular dynamics (MD) runs (Datasets B and C), and 500 MD snapshots of the 25 elements Cantor-style alloy surface slabs. We also provide the HEA25-4-NN and HEA25S-4-NN final models, ...

Latest version: v2
Publication date: Mar 04, 2024

Phonon promoted charge density wave in topological kagome metal ScV₆Sn₆


Yong Hu, Junzhang Ma, Yinxiang Li, Yuxiao Jiang, Dariusz Jakub Gawryluk, Tianchen Hu, Jérémie Teyssier, Volodymyr Multian, Zhouyi Yin, Shuxiang Xu, Soohyeon Shin, Igor Plokhikh, Xinloong Han, Nicholas C. Plumb, Yang Liu, Jia-Xin Yin, Zurab Guguchia, Yue Zhao, Andreas P. Schnyder, Xianxin Wu, Ekaterina Pomjakushina, M. Zahid Hasan, Nanlin Wang, Ming Shi

  • Charge density wave (CDW) orders in vanadium-based kagome metals have recently received tremendous attention, yet their origin remains a topic of debate. The discovery of ScV₆Sn₆, a bilayer kagome metal featuring an intriguing √3 x √3 x 3 CDW order, offers a novel platform to explore the underlying mechanism behind the unconventional CDW. Here, we combine high-resolution angle-resolved photoemission spectroscopy, Raman scattering and density functional theory to investigate the electronic structure and phonon modes of ScV₆Sn₆. We identify topologically nontrivial surface states and multiple van Hove singularities (VHSs) in the vicinity of the Fermi level, with one VHS aligning with the in-plane component of the CDW vector near the K ̅ point. Additionally, Raman measurements indicate a strong electron-phonon coupling, as evidenced by a two-phonon mode and new emergent modes. Our findings highlight the fundamental role of lattice degrees of freedom in promoting the CDW in ScV₆Sn₆.

Latest version: v1
Publication date: Mar 03, 2024

Mechanism of charge transport in lithium thiophosphate


Lorenzo Gigli, Davide Tisi, Federico Grasselli, Michele Ceriotti

  • Lithium ortho-thiophosphate (Li₃PS₄) has emerged as a promising candidate for solid-state-electrolyte batteries, thanks to its highly conductive phases, cheap components, and large electrochemical stability range. Nonetheless, the microscopic mechanisms of Li-ion transport in Li₃PS₄ are far to be fully understood, the role of PS₄ dynamics in charge transport still being controversial. We build machine learning potentials targeting state-of-the-art DFT references (PBEsol, r²SCAN, and PBE0) to tackle this problem in all known phases of Li₃PS₄ (α, β and γ), for large system sizes and timescales. We discuss the physical origin of the observed superionic behavior of Li₃PS₄: the activation of PS₄ flipping drives a structural transition to a highly conductive phase, characterized by an increase of Li-site availability and by a drastic reduction in the activation energy of Li-ion diffusion. We also rule out any paddle-wheel effects of PS₄ tetrahedra in the superionic phases–previously ...

Latest version: v2
Publication date: Mar 01, 2024

Predicting polymerization reactions via transfer learning using chemical language models


Brenda S. Ferrari, Matteo Manica, Ronaldo Giro, Teodoro Laino, Mathias B. Steiner

  • Polymers are candidate materials for a wide range of sustainability applications such as carbon capture and energy storage. However, computational polymer discovery lacks automated analysis of reaction pathways and stability assessment through retro-synthesis. Here, we report the first extension of transformer-based language models to polymerization reactions for both forward and retrosynthesis tasks. We curated a polymerization dataset for vinyl polymers covering reactions and retrosynthesis for representative homo-polymers and co-polymers. Overall, we report a forward model accuracy of 80% and a backward model accuracy of 60%. We further analyse the model performance on a set of case studies by providing polymerization and retro-synthesis examples and evaluating the model’s predictions quality from a materials science perspective.

Latest version: v2
Publication date: Feb 29, 2024

Low-index mesoscopic surface reconstructions of Au surfaces using Bayesian force fields


Cameron Owen, Yu Xie, Anders Johansson, Lixin Sun, Boris Kozinsky

  • Metal surfaces have long been known to reconstruct, significantly influencing their structural and catalytic properties. Many key mechanistic aspects of these subtle transformations remain poorly understood due to limitations of previous simulation approaches. Using active learning of Bayesian machine-learned force fields trained from ab initio calculations, we enable large-scale molecular dynamics simulations to describe the thermodynamics and time evolution of the low-index mesoscopic surface reconstructions of Au (e.g., the Au(111)-`Herringbone,' Au(110)-(1x2)-`Missing-Row,' and Au(100)-`Quasi-Hexagonal' reconstructions). This capability yields direct atomistic understanding of the dynamic emergence of these surface states from their initial facets, providing previously inaccessible information such as nucleation kinetics and a complete mechanistic interpretation of reconstruction under the effects of strain and local deviations from the original stoichiometry. We successfully ...

Latest version: v1
Publication date: Feb 29, 2024

A bridge between trust and control: Computational workflows meet automated battery cycling


Peter Kraus, Edan Bainglass, Francisco F. Ramirez, Enea Svaluto-Ferro, Loris Ercole, Benjamin Kunz, Sebastiaan P. Huber, Nukorn Plainpan, Nicola Marzari, Corsin Battaglia, Giovanni Pizzi

  • Compliance with good research data management practices means trust in the integrity of the data, and it is achievable by a full control of the data gathering process. In this work, we demonstrate tooling which bridges these two aspects, and illustrate its use in a case study of automated battery cycling. We successfully interface off-the-shelf battery cycling hardware with the computational workflow management software AiiDA, allowing us to control experiments, while ensuring trust in the data by tracking its provenance. We design user interfaces compatible with this tooling, which span the inventory, experiment design, and result analysis stages. Other features, including monitoring of workflows and import of externally generated and legacy data are also implemented. Finally, the full software stack required for this work is made available in a set of open-source packages.

Latest version: v2
Publication date: Feb 29, 2024

Unraveling the crystallization kinetics of the Ge₂Sb₂Te₅ phase change compound with a machine-learned interatomic potential


Omar Abou El Kheir, Luigi Bonati, Michele Parrinello, Marco Bernasconi

  • The phase change compound Ge₂Sb₂Te₅ (GST225) is exploited in advanced non-volatile electronic memories and in neuromorphic devices which both rely on a fast and reversible transition between the crystalline and amorphous phases induced by Joule heating. The crystallization kinetics of GST225 is a key functional feature for the operation of these devices. We report here on the development of a machine-learned interatomic potential for GST225 that allowed us to perform large scale molecular dynamics simulations (over 10000 atoms for over 100 ns) to uncover the details of the crystallization kinetics in a wide range of temperatures of interest for the programming of the devices. The potential is obtained by fitting with a deep neural network (NN) scheme a large quantum-mechanical database generated within Density Functional Theory. The availability of a highly efficient and yet highly accurate NN potential opens the possibility to simulate phase change materials at the length and time scales of the real devices.

Latest version: v2
Publication date: Feb 22, 2024

Probing the Mott-insulating behavior of Ba₂MgReO₆ with DFT+DMFT


Maximilian E. Merkel, Aria Mansouri Tehrani, Claude Ederer

  • We investigate the interplay of spin-orbit coupling, electronic correlations, and lattice distortions in the 5d¹ double perovskite Ba₂MgReO₆. Combining density-functional theory (DFT) and dynamical mean-field theory (DMFT), we establish the Mott-insulating character of Ba₂MgReO₆ in both its cubic and tetragonal paramagnetic phases. Despite substantial spin-orbit coupling, its impact on the formation of the insulating state is minimal, consistent with theoretical expectations for d¹ systems. We further characterize the electronic properties of the cubic and tetragonal phases by analyzing spectral functions and local occupations in terms of multipole moments centered on the Re sites. Our results confirm the presence of ferroically ordered z² quadrupoles in addition to the antiferroic x²-y²-type order. We compare two equivalent but complementary descriptions in terms of either effective Re-t2g frontier orbitals or more localized atomic-like Re-d and O-p orbitals. The former maps ...

Latest version: v1
Publication date: Feb 22, 2024

Electronic excited states from physically-constrained machine learning


Edoardo Cignoni, Divya Suman, Jigyasa Nigam, Lorenzo Cupellini, Benedetta Mennucci, Michele Ceriotti

  • Data-driven techniques are increasingly used to replace electronic-structure calculations of matter. In this context, a relevant question is whether machine learning (ML) should be applied directly to predict the desired properties or be combined explicitly with physically-grounded operations. We present an example of an integrated modeling approach, in which a symmetry-adapted ML model of an effective Hamiltonian is trained to reproduce electronic excitations from a quantum-mechanical calculation. The resulting model can make predictions for molecules that are much larger and more complex than those that it is trained on, and allows for dramatic computational savings by indirectly targeting the outputs of well-converged calculations while using a parameterization corresponding to a minimal atom-centered basis. Our results on a comprehensive dataset of hydrocarbons emphasize the merits of intertwining data-driven techniques with physical approximations, improving the ...

Latest version: v2
Publication date: Feb 20, 2024

Kapitza stabilization of quantum critical order


Dushko Kuzmanovski, Jonathan Schmidt, Nicola A. Spaldin, Hendrik M. Rønnow, Gabriel Aeppli, Alexander V. Balatsky

  • Dynamical perturbations modify the states of classical systems in surprising ways and give rise to important applications in science and technology. For example, Floquet engineering exploits the possibility of band formation in the frequency domain when a strong, periodic variation is imposed on parameters such as spring constants. We describe here Kapitza engineering, where a drive field oscillating at a frequency much higher than the characteristic frequencies for the linear response of a system changes the potential energy surface so much that maxima found at equilibrium become local minima, in precise analogy to the celebrated Kapitza pendulum where the unstable inverted configuration, with the mass above rather than below the fulcrum, actually becomes stable. Our starting point is a quantum field theory of the Ginzburg-Devonshire type, suitable for many condensed matter systems, including particularly ferroelectrics and quantum paralectrics such as the common substrate (for ...

Latest version: v1
Publication date: Feb 20, 2024

Searching for the thinnest metallic wire


Chiara Cignarella, Davide Campi, Nicola Marzari

  • One-dimensional materials have gained much attention in the last decades: from carbon nanotubes to ultrathin nanowires, to few-atom atomic chains, these can all display unique electronic properties and great potential for next-generation applications. Exfoliable bulk materials could naturally provide a source for one-dimensional wires with well defined structure and electronics. Here, we explore a database of one-dimensional materials that could be exfoliated from experimentally known three-dimensional Van-der-Waals compounds, searching metallic wires that are resilient to Peierls distortions and could act as vias or interconnects for future downscaled electronic devices. As the one-dimensional nature makes these wires particularly susceptible to dynamical instabilities, we carefully characterise vibrational properties to identify stable phases and characterize electronic and dynamical properties. Our search identifies several novel and stable wires; notably, we identify what ...

Latest version: v2
Publication date: Feb 15, 2024

On-surface cyclization of vinyl groups on poly-para-phenylene involving an unusual pentagon to hexagon transformation


Marco Di Giovannantonio, Zijie Qiu, Carlo A. Pignedoli, Sobi Asako, Pascal Ruffieux, Klaus Müllen, Akimitsu Narita, Roman Fasel

  • On-surface synthesis relies on carefully designed molecular precursors that are thermally activated to afford desired, covalently coupled architectures. In a recent publication, we studied the reactions of vinyl groups on poly-para-phenylene and provided a comprehensive description of all the reaction steps taking place on the Au(111) surface under ultrahigh vacuum conditions. We find that vinyl groups successfully cyclize with the phenylene rings in the ortho positions, forming a dimethyl-dihydroindenofluorene as the repeating unit, which can be further dehydrogenated to a dimethylene-dihydroindenofluorene structure. Interestingly, the obtained polymer can be transformed cleanly into thermodynamically stable polybenzo[k]tetraphene at higher temperature, involving a previously elusive pentagon-to-hexagon transformation via ring opening and rearrangement on a metal surface. Our insights into the reaction cascade unveil fundamental chemical processes involving vinyl groups on ...

Latest version: v1
Publication date: Feb 15, 2024

Depth-dependent time reversal symmetry breaking response in the charge-ordered kagome material RbV₃Sb₅


J.N. Graham, C. Mielke III, D. Das, T. Morresi, V. Ardakani, A. Suter, T. Prokscha, H. Deng, R. Khasanov, S. D. Wilson, A. C. Salinas, Y. Zhong, K. Okazaki, Z. Wang, M. Z. Hasan, M. Fisher, T. Neupert, J.-X. Yin, S. Sanna, H. Luetkens, Z. Salman, P. Bonfà, Z. Guguchia

  • The AV₃Sb₅ kagome superconductors series are of intense interest due to their diverse and intricate properties. The breaking of time-reversal symmetry (TRS) in the normal state of these superconductors stands as a significant feature, yet the extent to which this effect can be tuned remains uncertain. Here, we employ a unique low-energy muon spin rotation technique combined with local field numerical analysis to study the TRS breaking response as a function of depth from the surface in single crystals of RbV₃Sb₅ with charge order and Cs(V0.86Ta0.14)₃Sb₅ without charge order. In the bulk (specifically above 30 nm from the sur face) of RbV₃Sb₅, we have detected a notable increase in the internal field width experienced by the muon ensemble. This increase occurs within the charge ordered state. Intriguingly, the muon spin relaxation rate is significantly enhanced near the surface of RbV₃Sb₅ (specifically within a depth range of 30-40 nm from the surface), and ...

Latest version: v1
Publication date: Feb 15, 2024

Characterization of single in situ prepared interfaces composed of niobium and a selectively-grown (Bi1-xSbx)2Te3 topological insulator nanoribbon


Kevin Janßen, Philipp Rüßmann, Sergej Liberda, Michael Schleenvoigt, Xiao Hou, Abdur Rehman Jalil, Florian Lentz, Stefan Trellenkamp, Benjamin Bennemann, Erik Zimmermann, Gregor Mussler, Peter Schüffelgen, Claus-Michael Schneider, Stefan Blügel, Detlev Grützmacher, Lukasz Plucinski, Thomas Schäpers

  • With increasing interest in Majorana physics for possible quantum bit applications, a large interest has been developed to understand the properties of the interface between a s-type superconductor and a topological insulator. Up to this point the interface analysis was mainly focused on in-situ prepared Josephson junctions, which consist of two coupled single interfaces or to ex-situ fabricated single interface devices. In our work we utilize a novel fabrication process, combining selective area growth and shadow evaporation which allows the characterization of a single in-situ fabricated Nb/(Bi0.15Sb0.85)2Te3 nano interface. The resulting high interface transparency, is apparent by a zero bias conductance increase by a factor of 1.7. Furthermore, we present a comprehensive differential conductance analysis of our single in-situ interface for various magnetic fields, temperatures and gate voltages. Additionally, density functional ...

Latest version: v3
Publication date: Feb 15, 2024

Absolute energy levels of liquid water from many-body perturbation theory with effective vertex corrections


Alexey Tal, Thomas Bischoff, Alfredo Pasquarello

  • We demonstrate the importance of addressing the 𝚪 vertex and thus going beyond the GW approximation for achieving the energy levels of liquid water in many- body perturbation theory. In particular, we consider an effective vertex function in both the polarizability and the self-energy, which does not produce any computational overhead compared with the GW approximation. We yield the band gap, the ionization potential, and the electron affinity in good agreement with experiment and with a hybrid functional description. The achieved electronic structure and dielectric screening further lead to a good description of the optical absorption spectrum, as obtained through the solution of the Bethe–Salpeter equation. In particular, the experimental peak position of the exciton is accurately reproduced.

Latest version: v1
Publication date: Feb 14, 2024

Crystallization kinetics of nanoconfined GeTe slabs in GeTe/TiTe-like superlattices for phase change memories


Debdipto Acharya, Omar Abou El Kheir, Davide Campi, Marco Bernasconi

  • Superlattices made of alternating blocks of the phase change compound Sb₂Te₃ and of TiTe₂ confining layers have been recently proposed for applications in neuromorphic devices. The Sb₂Te₃/TiTe₂ heterostructure allows for a better control of multiple intermediate resistance states and for a lower drift with time of the electrical resistance of the amorphous phase. However, Sb₂Te₃ suffers from a low data retention due to a low crystallization temperature Tx. Substituting Sb₂Te₃ with a phase change compound with a higher Tx, such as GeTe, seems an interesting option in this respect. Nanoconfinement might, however, alters the crystallization kinetics with respect to the bulk. In this work, we investigated the crystallization process of GeTe nanoconfined in geometries mimicking GeTe/TiTe₂ superlattices by means of molecular dynamics simulations with a machine learning potential. The simulations reveal that nanoconfinement induces a mild reduction in the crystal ...

Latest version: v2
Publication date: Feb 12, 2024

Anomalously low vacancy formation energies and migration barriers at Cu/AlN interfaces from ab initio calculations


Yann Muller, Andrej Antusek, Lars Jeurgens, Vladyslav Turlo

  • It is well known that interfaces in nanomaterials can act as ultra-fast short-circuit diffusion paths, as originating from local structural, chemical and/or electronic modifications at the interface. For example, the interface diffusivity of Cu in Cu/AlN nanomultilayers can be up to two orders of magnitude higher as compared to the bulk, which may promote interfacial premelting of Cu. Extensive ab initio calculations of vacancy formation and migration energies in Cu/AlN nanomultilayers were performed to arrive at the fundamental understanding of such anomalously fast interface diffusion phenomena. It was found that both the metallic Al-terminated interface and the mixed-bonded N-terminated interface promote high atomic interface mobilities by lowering the vacancy formation and vacancy migration energies in the interfacial Cu planes. Moreover, the out-of-plane vacancy migration energies highlights a strong tendency of vacancy segregation toward both interfaces.

Latest version: v1
Publication date: Feb 08, 2024

On-surface synthesis of anthracene-fused zigzag graphene nanoribbons from 2,7-dibromo-9,9'-bianthryl reveals unexpected ring rearrangements


Xiushang Xu, Amogh Kinikar, Marco Di Giovannantonio, Carlo Antonio Pignedoli, Pascal Ruffieux, Klaus Müllen, Roman Fasel, Akimitsu Narita

  • On-surface synthesis has emerged as a powerful strategy to fabricate unprecedented forms of atomically precise graphene nanoribbons (GNRs). However, the on-surface synthesis of zigzag GNRs (ZGNR) has met with only limited success. In the paper where the data are discussed, we report the synthesis and on-surface reactions of 2,7-dibromo-9,9'-bianthryl as the precursor towards π-extended ZGNRs. Characterization by scanning tunneling microscopy and high-resolution noncontact atomic force microscopy clearly demonstrated the formation of anthracene-fused ZGNRs. Unique skeletal rearrangements were also observed, which could be explained by intramolecular Diels-Alder cycloaddition. Theoretical calculations of the electronic properties of the anthracene-fused ZGNRs revealed spin-polarized edge-states and a narrow bandgap of 0.20 eV.

Latest version: v1
Publication date: Feb 08, 2024

Microscopic nature of the charge-density wave in the kagome superconductor RbV₃Sb₅


Jonathan Frassineti, Pietro Bonfà, Giuseppe Allodi, Erik Garcia, Rong Cong, Brenden R. Ortiz, Stephen D. Wilson, Roberto De Renzi, Vesna F. Mitrović, Samuele Sanna

  • The recently discovered vanadium-based Kagome metals AV₃Sb₅ (A = K, Rb, Cs) undergo a unique phase transition into charge-density wave (CDW) order which precedes both unconventional superconductivity and time-reversal symmetry breaking. Therefore the essential first step in building a full understanding of the role of CDW in establishing these unconventional phases is to unveil the symmetries and the microscopic nature of the charge-ordered phase. Here, we determine the exact structure of the 2×2×2 superlattice that develops below the charge-density wave ordering temperature (TCDW) in RbV₃Sb₅. We present a comprehensive set of ⁵¹V, ⁸⁷Rb, and ¹²¹Sb nuclear magnetic resonance (NMR) measurements and density functional theory simulations of NMR observables to provide a unique site-selective view into the local nature of the charge-ordered phase. The combination of these experimental results with simulations provides compelling evidence that the CDW structure prevailing below 103 K in ...

Latest version: v1
Publication date: Feb 05, 2024

Dynamics of the charge transfer to solvent process in aqueous iodide


Jinggang Lan, Majed Chergui, Alfredo Pasquarello

  • Charge-transfer-to-solvent states in aqueous halides are ideal systems for studying the electron-transfer dynamics to the solvent involving a complex interplay between electronic excitation and solvent polarization. Despite extensive experimental investigations, a full picture of the charge-transfer-to-solvent dynamics has remained elusive. Here, we visualise the intricate interplay between the dynamics of the electron and the solvent polarization occurring in this process. Through the combined use of ab initio molecular dynamics and machine learning methods, we investigate the structure, dynamics and free energy as the excited electron evolves through the charge-transfer-to-solvent process, which we characterize as a sequence of states denoted charge-transfer-to-solvent, contact-pair, solvent-separated, and hydrated electron states, depending on the distance between the iodine and the excited electron. Our assignment of the charge-transfer-to-solvent states is supported by the ...

Latest version: v1
Publication date: Feb 05, 2024

Different ordering temperature of the Mn antisite sublattice in the intrinsic magnetic topological insulators of the MnBi₂Te₄ family


Manaswini Sahoo, Ifeanyi John Onuorah, Laura Christina Folkers, Evgueni Vladimirovich Chulkov, Mikhail M. Otrokov, Ziya S. Aliev, Imamaddin R. Amiraslanov, Anja Wolter-Giraud, Bernd Büchner, Laura Teresa Corredor Bohorquez, Chennan Wang, Zaher Salman, Anna Isaeva, Roberto De Renzi, Giuseppe Allodi

  • Magnetic topological insulators (TIs) promise a wealth of applications in spin-based technologies, relying on the novel quantum phenomena provided by their topological properties. Particularly promising is the (MnBi₂Te₄)(Bi₂Te₃)n layered family of established intrinsic magnetic TIs that can flexibly realize various magnetic orders and topological states. High tunability of this material platform is enabled by manganese–pnictogen intermixing, whose amounts and distribution patterns are controlled by synthetic conditions. Positive implication of the strong intermixing in MnSb₂Te₄ is the interlayer exchange coupling switching from antiferromagnetic to ferromagnetic, and the increasing magnetic critical temperature. On the other side, intermixing also implies atomic disorder which may be detrimental for applications. Here we employ nuclear magnetic resonance and muon spin spectroscopy, sensitive local probe techniques, to scrutinize the impact of the intermixing on the ...

Latest version: v1
Publication date: Jan 31, 2024

On-site and inter-site Hubbard corrections in magnetic monolayers: The case of FePS₃ and CrI₃


Fatemeh Haddadi, Edward Linscott, Iurii Timrov, Nicola Marzari, Marco Gibertini

  • Hubbard-corrected density-functional theory has proven to be successful in addressing self-interaction errors in 3D magnetic materials. However, the effectiveness of this approach for 2D magnetic materials has not been extensively explored. Here, we use PBEsol+U and its extensions PBEsol+U+V to investigate the electronic, structural, and vibrational properties of 2D antiferromagnetic FePS₃ and ferromagnetic CrI₃, and compare the monolayers with their bulk counterparts. Hubbard parameters (on-site U and inter-site V) are computed self-consistently using density-functional perturbation theory, thus avoiding any empirical assumptions. We show that for FePS₃ the Hubbard corrections are crucial in obtaining the experimentally observed insulating state with the correct crystal symmetry, providing also vibrational frequencies in good agreement with Raman experiments. While empirical U can lead to an unstable ground-state (i.e. imaginary phonons), the system remains stable through the ...

Latest version: v1
Publication date: Jan 30, 2024

The role of oxidizing conditions in the dispersion of supported platinum nanoparticles explored by ab initio modeling


Agustin Salcedo, Anastassia N. Alexandrova, David Loffreda, Carine Michel

  • Achieving fine control over the dispersion of supported platinum nanoparticles (Pt) is a promising avenue to enhance their catalytic activity and selectivity. Experimental observations suggest that exposing ceria-supported Pt nanoparticles to O₂ at 500 °C promote their dispersion into smaller particles and eventually single atoms. In the associated paper we have combined several approaches and types of models in a consistent atomistic framework to evaluate the relative stability of ceria-supported Pt as a function of the degree of oxidation of Pt and of the particle size, ranging from single atoms to nanoparticles of 1.5 nm of diameter.

Latest version: v1
Publication date: Jan 29, 2024

An overview of the spin dynamics of antiferromagnetic Mn₅Si₃


N. Biniskos, F. J. dos Santos, M. dos Santos Dias, S. Raymond, K. Schmalzl, P. Steffens, J. Persson, N. Marzari, S. Blügel, S. Lounis, T. Brückel

  • The metallic compound Mn5Si3 hosts a series of antiferromagnetic phases that can be controlled by external stimuli, such as temperature and magnetic field. In this work, we investigate the spin-excitation spectrum of bulk Mn5Si3 by combining inelastic neutron scattering measurements and density functional theory calculations. We study the evolution of the dynamical response under external parameters and demonstrate that the spin dynamics of each phase is robust against any combination of temperature and magnetic field. In particular, the high-energy spin dynamics is very characteristic of the different phases consisting of either spin waves or broad fluctuation patterns. This data set contains the data relevant to performing the spin dynamics simulations with the Spirit code, the spin-wave calculations with the SWIS code, and the neutron scattering experimental data.

Latest version: v1
Publication date: Jan 29, 2024

Interfacial fluid rheology of soft particles


Maximilian M. Schmidt, José Ruiz-Franco, Steffen Bochenek, Fabrizio Camerin, Emanuela Zaccarelli, Andrea Scotti

  • In situ interfacial rheology and numerical simulations are used to investigate microgel monolayers in a wide range of packing fractions, ζ2D. The heterogeneous particle compressibility determines two flow regimes characterized by distinct master curves. To mimic the microgel architecture and reproduce experiments, an interaction potential combining a soft shoulder with the Hertzian model is introduced. In contrast to bulk conditions, the elastic moduli vary nonmonotonically with ζ2D at the interface, confirming long-sought predictions of reentrant behavior for Hertzian-like systems.

Latest version: v1
Publication date: Jan 24, 2024

Calculation of screened Coulomb interaction parameters for the charge-disproportionated insulator CaFeO₃


Maximilian E. Merkel, Claude Ederer

  • We calculate the screened electron-electron interaction for the charge-disproportionated insulator CaFeO₃ using the constrained random-phase approximation (cRPA). While in many correlated materials, the formation of a Mott-insulating state is driven by a large local Coulomb repulsion, represented by the Hubbard U, several cases have been identified more recently where U is strongly screened and instead the Hund's interaction J dominates the physics. Our results confirm a strong screening of the local Coulomb repulsion U in CaFeO₃ whereas J is much less screened and can thus stabilize a charge-disproportionated insulating state. This is consistent with the case of the rare-earth nickelates where similar behavior has been demonstrated. In addition, we validate some common assumptions used for parametrizing the local electron-electron interaction in first-principles calculations based on density-functional theory (DFT), assess the dependence of the interaction on the choice of ...

Latest version: v1
Publication date: Jan 24, 2024

Auxetic polymer networks: The role of crosslinking, density, and disorder


Andrea Ninarello, José Ruiz-Franco, Emanuela Zaccarelli

  • Low-crosslinked polymer networks have recently been found to behave auxetically when subjected to small tensions, that is, their Poisson’s ratio ν becomes negative. In addition, for specific state points, numerical simulations revealed that diamond-like networks reach the limit of mechanical stability, exhibiting values of ν = −1, a condition that we define as hyper-auxeticity. This behavior is interesting per se for its consequences in materials science but is also appealing for fundamental physics because the mechanical instability is accompanied by evidence of criticality. In this work, we deepen our understanding of this phenomenon by performing a large set of equilibrium and stress–strain simulations in combination with phenomenological elasticity theory. The two approaches are found to be in good agreement, confirming the above results. We also extend our investigations to disordered polymer networks and find that the hyper-auxetic behavior also holds in this case, still ...

Latest version: v1
Publication date: Jan 24, 2024

Deep learning of surface elastic chemical potential in strained films: from statics to dynamics


Luis Martín-Encinar, Daniele Lanzoni, Andrea Fantasia, Fabrizio Rovaris, Roberto Bergamaschini, Francesco Montalenti

  • We develop a convolutional neural network (NN) approach able to predict the elastic contribution to chemical potential μₑ at the surface of a 2D strained film given its profile h(x). Arbitrary h(x) profiles are obtained by using a Perlin Noise generator and the corresponding μₑ profiles are calculated either by a Green's function approximation (GA) or by Finite Element Method (FEM). First, a large dataset is produced by exploiting the GA method and it is then used for the training of the NN model. The performance of the trained NN is extensively examined, demonstrating its ability to predict μₑ looking both to the training/validation set and to an additional testing set containing different profiles, including sinusoids, gaussians and sharp peaks never considered in the NN training. The NN is then applied to simulate the morphological evolution of strained Ge films, where the predicted μₑ at each integration timestep plays the role of driving force for material redistribution in ...

Latest version: v2
Publication date: Jan 23, 2024

Understanding the role of oxygen-vacancy defects in Cu₂O(111) from first-principle calculations


Nanchen Dongfang, Marcella Iannuzzi, Yasmine Al-Hamdani

  • The presence of defects, such as copper and oxygen vacancies, in cuprous oxide films determines their characteristic carrier conductivity and consequently their application as semiconducting systems. There are still open questions on the induced electronic re-distribution, including the formation of polarons. Indeed, to accurately reproduce the structural and electronic properties at the cuprous oxide surface, very large slab models and theoretical approaches that go beyond the standard generalized gradient corrected density functional theory are needed. In this work we investigate oxygen vacancies formed in proximity of a reconstructed Cu₂O(111) surface, where the outermost unsaturated copper atoms are removed, thus forming non-stoichiometric surface layers with copper vacancies. We address simultaneously surface and bulk properties by modelling a thick and symmetric slab, to find that hybrid exchange-correlation functionals are needed to describe the oxygen vacancy in this ...

Latest version: v1
Publication date: Jan 15, 2024

On-surface interchain coupling and skeletal rearrangement of indenofluorene polymers


Qiang Chen, Marco Di Giovannantonio, Kristjan Eimre, José I. Urgel, Pascal Ruffieux, Carlo A. Pignedoli, Klaus Müllen, Roman Fasel, Akimitsu Narita

  • On-surface synthesis serves as a powerful approach to construct π-conjugated carbon nanostructures that are not accessible by conventional wet chemistry. Nevertheless, this method has been limited by the types and numbers of available on-surface transformations. While the majority of successful cases exploit thermally triggered dehalogenative carbon–carbon coupling and cyclodehydrogenation, rearrangement of appropriate functional moieties has received limited research attention. In a recent work, we describe the unprecedented interchain coupling and thermally induced skeleton rearrangement of (dihydro)indeno[2,1-b]fluorene (IF) polymers on an Au(111) surface under ultrahigh vacuum conditions, leading to different ladder polymers as well as fully fused graphene nanoribbon segments containing pentagonal and heptagonal rings. Au-coordinated nanoribbons are also observed. All structures are unambiguously characterized by high-resolution scanning probe microscopy. The results provide ...

Latest version: v1
Publication date: Jan 09, 2024

Ambipolar charge transfer of larger fullerenes enabled by the modulated surface potential of h-BN/Rh(111)


Max Bommert, Bruno Schuler, Carlo A. Pignedoli, Roland Widmer, Oliver Gröning

  • A detailed understanding of how molecules interact with two-dimensional materials, particularly concerning energy level alignment and charge transfer processes, is essential to incorporate functional molecular films into next-generation 2D material-organic hybrid devices. One of the major challenges in integrating molecular films in field-effect transistors is facilitating ambipolar charge transport, which is often hindered by the large electronic gap of the organic layers. In a recent work we compare the adsorption site-dependent energy level alignment of C60, C70, and C84 fullerenes induced by the spatial variation of the electrostatic surface potential of the h-BN/Rh(111) Moiré superstructure. As the size of the fullerenes increases, the HOMO-LUMO gap shrinks. In the case of C84, we find an intrinsic charge transfer from the substrate to the fullerenes adsorbed in the Moiré pore centers, rendering them negatively charged. The electric field effect-induced charging of neutral ...

Latest version: v1
Publication date: Jan 09, 2024

Solute strengthening of prism edge dislocations in Mg alloys


Masoud Rahbar Niazi, W. A Curtin

  • The poor ductility of hcp Mg is attributed to the low activity of non-basal slip systems and so activation of prismatic slip can aid ductility in rolled sheets by providing three additional <a> Burgers vector slip systems. Experimental studies show that dilute additions of alloying elements such as Zn and Al leads to softening of prismatic slip at low temperatures but strengthening at higher temperatures. Here, the role of solute strengthening of prismatic edge dislocations is investigated as a possible explanation for the higher-T strengthening. Mg-Zn is studied using first-principles inputs in a parameter-free solute strengthening theory. First-principles DFT is necessary to accurately assess the strong solute chemical interaction energies in the core of the compact edge dislocation. Such calculations are subtle due to motion of the dislocation in the presence of the solute, and methods to obtain reliable results with acceptable computational cost are discussed. While ...

Latest version: v1
Publication date: Jan 09, 2024

Systematic determination of a material’s magnetic ground state from first principles


Andres Tellez-Mora, Xu He, Eric Bousquet, Ludger Wirtz, Aldo Romero

  • We present a self-consistent method based on first-principles calculations to determine the magnetic ground state of materials, regardless of their dimensionality. Our methodology is founded on satisfying the stability conditions derived from the linear spin wave theory (LSWT) by optimizing the magnetic structure iteratively. We demonstrate the effectiveness of our method by successfully predicting the experimental magnetic structures of NiO, FePS₃, FeP, MnF₂, FeCl₂, and CuO. In each case, we compared our results with available experimental data and existing theoretical calculations reported in the literature. Finally, we discuss the validity of the method and the possible extensions.

Latest version: v1
Publication date: Jan 08, 2024

Emergence of threefold symmetric helical photocurrents in epitaxial low twinned Bi₂Se₃


Blair Connelly, Patrick Taylor, George de Coster

  • We present evidence of a strong circular photon drag effect (PDE) in topological insulators (TIs) through the observation of threefold rotationally symmetric helicity-dependent topological photocurrents using THz spectroscopy in epitaxially-grown Bi₂Se₃ with reduced crystallographic twinning. We establish how twinned domains introduce competing nonlinear optical (NLO) responses inherent to the crystal structure that obscure geometry-sensitive optical processes through the introduction of a spurious mirror symmetry. Minimizing the twinning defect reveals strong NLO response currents whose magnitude and direction depend on the alignment of the excitation to the crystal axes and follow the threefold rotational symmetry of the crystal. Notably, photocurrents arising from helical light reverse direction for left/right circular polarizations and maintain a strong azimuthal dependence—a result uniquely attributable to the circular PDE, where the photon momentum acts as an applied ...

Latest version: v1
Publication date: Jan 05, 2024

Crossover from Boltzmann to Wigner thermal transport in thermoelectric skutterudites


Enrico Di Lucente, Michele Simoncelli, Nicola Marzari

  • Skutterudites are crystals with a cagelike structure that can be augmented with filler atoms (“rattlers”), usually leading to a reduction in thermal conductivity that can be exploited for thermoelectric applications. Here, we leverage the recently introduced Wigner formulation of thermal transport to elucidate the microscopic physics underlying heat conduction in skutterudites, showing that filler atoms can drive a crossover from the Boltzmann to the Wigner regimes of thermal transport, i.e., from particlelike conduction to wavelike tunneling. At temperatures where the thermoelectric efficiency of skutterudites is largest, wavelike tunneling can become comparable to particlelike propagation. We define a Boltzmann deviation descriptor able to differentiate the two regimes and relate the competition between the two mechanisms to the materials' chemistry, providing a design strategy to select rattlers and identify optimal compositions for thermoelectric applications.

Latest version: v1
Publication date: Jan 05, 2024

Screening of low-friction two-dimensional materials from high-throughput calculations using frictional figure of merit


Kewei Tang, Weihong Qi, Guoliang Ru, Weimin Liu

  • Two-dimensional materials are excellent lubricants with inherent advantages. However, superlubricity has only been reported in a few of them. It is a regret that other promising 2D materials with different physical properties cannot be discovered and applied in production so that energy consumption can be greatly reduced. Here we carry out high-throughput calculations for 1475 two-dimensional materials and screen for low-friction ones. To set a standard, we propose, for the first time, a geometry-independent frictional figure of merit based on the condition for stick-slip transition and our theory of Moiré friction. For the efficient calculation of this figure of merit, an innovative approach is developed based on an improved registry index model. Through the calculation, 340 materials are found to have a figure of merit lower than 10-3. Eventually, a small set of 21 materials with a figure of merit lower than 10-4 are screened out within them. These materials can provide ...

Latest version: v1
Publication date: Dec 21, 2023

Sterically selective [3+3] cycloaromatization in the on-surface synthesis of nanographenes


Amogh Kinikar, Xiao-Ye Wang, Marco Di Giovannantonio, José I. Urgel, Pengcai Liu, Kristjan Eimre, Carlo Antonio Pignedoli, Samuel Stolz, Max Bommert, Shantanu Mishra, Qiang Sun, Roland Widmer, Zijie Qiu, Akimitsu Narita, Klaus Müllen, Pascal Ruffieux, Roman Fasel

  • Surface-catalyzed reactions have been used to synthesize carbon nanomaterials with atomically pre-defined structures. The recent discovery of a gold surface-catalyzed [3+3] cycloaromatization of isopropyl substituted arenes has enabled the on-surface synthesis of arylene-phenylene copolymers, where the surface activates the isopropyl substituents to form phenylene rings by intermolecular coupling. However, the resulting polymers suffered from undesired cross-linking when more than two molecules reacted at a single site. In the manuscript in which this data is discussed we show that such cross-links can be prevented through steric protection by attaching the isopropyl groups to larger arene cores. Upon thermal activation of isopropyl-substituted 8,9-dioxa-8a-borabenzo[fg]tetracene on Au(111), cycloaromatization is observed to occur exclusively between two molecules. The cycloaromatization intermediate formed by the covalent linking of two molecules is prevented from reacting with ...

Latest version: v1
Publication date: Dec 20, 2023

Water and Cu⁺ synergy in selective CO₂ hydrogenation to methanol over Cu/MgO catalysts


Estefanía Fernández Villanueva, Pablo Germán Lustemberg, Minjie Zhao, Jose Soriano, Patricia Concepción, María Verónica Ganduglia Pirovano

  • The CO₂ hydrogenation reaction to produce methanol holds great significance as it contributes to achieving a CO₂-neutral economy. Previous research identified isolated Cu⁺ species doping the oxide surface of a Cu-MgO-Al₂O₃ mixed oxide derived from a hydrotalcite precursor as the active site in CO₂ hydrogenation, stabilizing monodentate formate species as a crucial intermediate in methanol synthesis. In this work, we present a molecular-level understanding of how surface water and hydroxyl groups play a crucial role in facilitating spontaneous CO₂ activation at Cu⁺ sites and the formation of monodentate formate species. The computational evidence has been experimentally validated by comparing the catalytic performance of the Cu-MgO-Al₂O₃ catalyst with hydroxyl groups against its hydrophobic counterpart, where hydroxyl groups are blocked using an esterification method. Our work highlights the synergistic effect between doped Cu⁺ ions and adjacent hydroxyl groups, both of which serve ...

Latest version: v1
Publication date: Dec 20, 2023

Flat-band hybridization between f and d states near the Fermi energy of SmCoIn₅


David W. Tam, Nicola Colonna, Fatima Alarab, Vladimir Strocov, Dariusz Jakub Gawryluk, Ekaterina Pomjakushina, Michel Kenzelmann

  • We present high-quality angle-resolved photoemission (ARPES) and density functional theory calculations (DFT+U) of SmCoIn₅. We find broad agreement with previously published studies of LaCoIn₅ and CeCoIn₅, confirming that the Sm 4f electrons are mostly localized. Nevertheless, our model is consistent with an additional delocalized Sm component, stemming from hybridization between the 4f electrons and the metallic bands at “hot spot” positions in the Brillouin zone. The dominant hot spot, called γz, is similar to a source of delocalized f states found in previous experimental and theoretical studies of CeCoIn₅. In this work, we identify and focus on the role of geometric frustration in exploring the relationship between heavy quasiparticles and the magnetically ordered ground state of SmCoIn₅. Specifically, we find a globally flat band consisting of Co 3dxy/3dz2 orbital states near E = −0.7 eV, indicating a general role for geometric frustration in the “115” ...

Latest version: v1
Publication date: Dec 19, 2023

Reduction of interlayer interaction in multilayer stacking graphene with carbon nanotube insertion: Insights from experiment and simulation


Mingda Ding, Taiki Inoue, John Isaac Enriquez, Harry Handoko Halim, Yui Ogawa, Yoshitaka Taniyasu, Yuji Hamamoto, Yoshitada Morikawa, Yoshihiro Kobayashi

  • We insert carbon nanotubes (CNT) as nanospacers to modulate the microstructure of multilayer stacking graphene. Nanospacers can increase interlayer distance and reduce interlayer interaction. The graphene/CNT stacking structure is experimentally fabricated and Raman spectroscopy verifies the reduction in interlayer interaction within the stacking structure. Thus, we study the microstructure of the stacked graphene and CNTs by molecular dynamics simulation to systematically investigate the effect of CNT insertion. The distribution distance, size, and arrangement of the CNT can modulate the interlayer distance. The graphene/CNT stacking structure exhibits two stable configurations: the upper-layer suspension and interlayer adsorption.

Latest version: v1
Publication date: Dec 14, 2023

Massively parallel implementation of gradients within the Random Phase Approximation: Application to the polymorphs of benzene


Frederick Stein, Jürg Hutter

  • The Random-Phase approximation (RPA) provides an appealing framework for semi-local density functional theory. In its current formulation, it is cost-effective and has a better scaling behaviour compared to other wavefunction based correlation methods. To broaden the application field for RPA, it is necessary to have first order properties available. RPA nuclear gradients allow for structure optimizations and data sampling for machine learning applications. We report on an efficient implementation of RPA nuclear gradients for massively parallel computers. We apply the implementation to two polymorphs of the benzene crystal obtaining very good cohesive and relative energies. Different correction and extrapolation schemes are investigated for further improvement of the results and in order to estimate error bars.

Latest version: v2
Publication date: Dec 13, 2023

Reaction-agnostic featurization of bidentate ligands for Bayesian ridge regression of enantioselectivity


Alexandre A. Schoepfer, Ruben Laplaza, Matthew D. Wodrich, Jerome Waser, Clemence Corminboeuf

  • Chiral ligands are important components in asymmetric homogeneous catalysis, but their synthesis and screening can be both time-consuming and resource-intensive. Data-driven approaches, in contrast to screening procedures based on intuition, have the potential to reduce the time and resources needed for reaction optimization by more rapidly identifying an ideal catalyst. These approaches, however, are often non-transferable and cannot be applied across different reactions. To overcome this drawback, we introduce a general featurization strategy for bidentate ligands that is coupled with an automated feature selection pipeline and Bayesian ridge regression to perform multivariate linear regression modeling. This approach, which is applicable to any reaction, incorporates electronic, steric, and topological features (rigidity/flexibility, branching, geometry, constitution) and is well-suited for early-stage ligand optimization. Using only small datasets, our workflow capably ...

Latest version: v1
Publication date: Dec 12, 2023

SPAᴴM(a,b): encoding the density information from guess Hamiltonian in quantum machine learning representations


Ksenia R. Briling, Yannick Calvino Alonso, Alberto Fabrizio, Clemence Corminboeuf

  • Recently, we introduced a class of molecular representations for kernel-based regression methods — the spectrum of approximated Hamiltonian matrices (SPAᴴM) — that takes advantage of lightweight one-electron Hamiltonians traditionally used as an SCF initial guess. The original SPAᴴM variant is built from occupied-orbital energies (\ie, eigenvalues) and naturally contains all the information about nuclear charges, atomic positions, and symmetry requirements. Its advantages were demonstrated on datasets featuring a wide variation of charge and spin, for which traditional structure-based representations commonly fail. SPAᴴM(a,b), as introduced here, expands eigenvalue SPAᴴM into local and transferable representations. It relies upon one-electron density matrices to build fingerprints from atomic or bond density overlap contributions inspired from preceding state-of-the-art representations. The performance and efficiency of SPAᴴM(a,b) is assessed on the predictions for datasets of ...

Latest version: v1
Publication date: Dec 08, 2023

Dipolar spin wave packet transport in a van der Waals antiferromagnet


Yue Sun, Fanhao Meng, Changmin Lee, Aljoscha Soll, Hongrui Zhang, Ramamoorthy Ramesh, Jie Yao, Zdeněk Sofer, Joseph Orenstein

  • Antiferromagnets are promising platforms for transduction and transmission of quantum information via magnons — the quanta of spin waves — and they offer advantages over ferromagnets in regard to dissipation, speed of response, and robustness to external fields. Recently, transduction was shown in a van der Waals antiferromagnets, where strong spin-exciton coupling enables readout of the amplitude and phase of coherent magnons by photons of visible light. This discovery shifts the focus of research to transmission, specifically to exploring the nonlocal interactions that enable magnon wave packets to propagate. Here we demonstrate that magnon propagation is mediated by the long-range dipole-dipole interaction. This coupling is an inevitable consequence of fundamental electrodynamics, and as such, will likely mediate the propagation of spin at long wavelengths in the entire class of van der Waals magnets currently under investigation. Successfully identifying the mechanism of spin ...

Latest version: v1
Publication date: Dec 08, 2023

Engineering surface dipoles on mixed conducting oxides with ultra-thin oxide decoration layers


Matthäus Siebenhofer, Andreas Nenning, Christoph Rameshan, Peter Blaha, Jürgen Fleig, Markus Kubicek

  • This dataset includes all data presented in the figures of the main manuscript: XPS work function changes, ab-initio calculated work functions, O2p band center shifts, Densities of state for LSC and PCO, i-PLD results for LSC, LSF, STF and PCO, Densities of state for adsorbed O2 on differently decorated PCO surfaces. In this work, we investigated surface dipole changes which were induced by modification of mixed conducting surfaces with binary oxides via pulsed laser deposition.

Latest version: v1
Publication date: Dec 08, 2023

From organic fragments to photoswitchable catalysts: the off-on structural repository for transferable kernel-based potentials


Frédéric Célerse, Matthew D. Wodrich, Sergi Vela, Simone Gallarati, Raimon Fabregat, Veronika Juraskova, Clémence Corminboeuf

  • Structurally and conformationally diverse databases are needed to train accurate neural networks or kernel-based potentials capable of exploring the complex free energy landscape of flexible functional organic molecules. Curating such databases for species beyond “simple” drug-like compounds or molecules comprised of well-defined building blocks (e.g., peptides) is challenging, as it requires thorough chemical space mapping and evaluation of both chemical and conformational diversity. Here, we introduce the OFF–ON (Organic Fragments From Organocatalysts that are Non-modular) database, a repository of 7,869 equilibrium and 67,457 non--equilibrium geometries of organic compounds and dimers aimed at describing conformationally flexible functional organic molecules, with an emphasis on photoswitchable organocatalysts. The relevance of this database is then demonstrated by training a Local Kernel Regression model on a low-cost semiempirical baseline and comparing it with a PBE0-D3 ...

Latest version: v1
Publication date: Dec 08, 2023

Solute misfit and solute interaction effects on strengthening: A case study in AuNi


Binglun Yin, Linhan Li, Sophie Drescher, Sascha Seils, Shankha Nag, Jens Freudenberger, William Curtin

  • AuNi is a classic long-studied fcc alloy combining a very “large” atom (Au) and a very “small” atom (Ni), and the large atomic size misfits suggest very high strengthening. Here, AuNi is used as a model alloy for the testing of new strengthening theories in random alloys that include the effects of both size misfits and solute–solute interactions. Experimentally, AuNi samples are fabricated, characterized, and tested, and show no segregation after annealing at 900 °C and a very high yield strength of 769 MPa. Theoretically, the main inputs to the theory (alloy lattice and elastic constants, solute misfit volumes, energy fluctuations associated with slip in the presence of solute–solute interactions) are extracted from experiments or computed using first-principles DFT. The parameter-free prediction of the yield strength is 809 MPa, in very good agreement with experiments. Solute–solute interactions enhance the strength only moderately (13%), demonstrating that the strengthening is ...

Latest version: v1
Publication date: Dec 01, 2023

Understanding the role of Hubbard corrections in the rhombohedral phase of BaTiO₃


Garu Gebreyesus, Lorenzo Bastonero, Michele Kotiuga, Nicola Marzari, Iurii Timrov

  • We present a first-principles study of the low-temperature rhombohedral phase of BaTiO₃ using Hubbard-corrected density-functional theory. By employing density-functional perturbation theory, we compute the onsite Hubbard U for Ti(3d) states and the intersite Hubbard V between Ti(3d) and O(2p) states. We show that applying the onsite Hubbard U correction alone to Ti(3d) states proves detrimental, as it suppresses the Ti(3d)-O(2p) hybridization and drives the system towards a cubic phase. Conversely, when both onsite U and intersite V are considered, the localized character of the Ti(3d) states is maintained, while also preserving the Ti(3d)-O(2p) hybridization, restoring the rhombohedral phase of BaTiO₃. The generalized PBEsol+U+V functional yields good agreement with experimental results for the band gap and dielectric constant, while the optimized geometry is slightly less accurate compared to PBEsol. Zone-center phonon frequencies and Raman spectra are found to be significantly ...

Latest version: v1
Publication date: Nov 30, 2023

Directing CO₂ electroreduction pathways for selective C₂ product formation using single-site doped Cu catalysts


Zhengyuan Li, Peng Wang, Xiang Lyu, Vamsi Krishna Reddy Kondapalli, Shuting Xiang, Juan D. Jimenez, Lu Ma, Takeshi Ito, Tianyu Zhang, Jithu Raj, Yanbo Fang, Yaocai Bai, Jianlin Li, Alexey Serov, Vesselin Shanov, Anatoly I. Frenkel, Sanjaya D. Senanayake, Yang Shize, Thomas Senftle, Jingjie Wu

  • This dataset includes all the atomic coordinates of the optimized computational models from electronic structure calculations reported in the manuscript. In this work, we highlight that single-site noble metal dopants on the Cu surface can influence C–O bond dissociation in a key selectivity-determining intermediate (e.g., oxygen-bound *CH₂CHO), which in turn direct the post-C–C coupling pathways to ethylene versus ethanol. Combining theoretical and experimental analyses, we demonstrate that the favorability of C–O bond scission is controlled by the oxygen affinity of the metal dopant on the Cu catalyst. We find that the selectivity ratio of ethylene-to-ethanol displays a volcano relationship with respect to the oxygen binding strength on the doped surfaces.

Latest version: v1
Publication date: Nov 30, 2023

Mechanism of thermally-activated prismatic slip in Mg


Xin Liu, William Curtin

  • Prismatic slip of the screw <a> dislocation in magnesium at temperatures ≳ 150 K is understood to be governed by double-cross-slip of the stable basal screw through the unstable prism screw and back to the basal screw, with the activation energy controlled by the formation energy of two basal-basal kinks. However, atomistic studies of the double-kink process predict activation energies roughly twice those derived experimentally. Here, a new mechanism of prism glide is proposed, analyzed theoretically, and demonstrated qualitatively and quantitatively via direct molecular dynamics (MD) simulations. The new mechanism is intrinsically 3d, and involves the nucleation of a single kink at the junction where a 3d prismatic dislocation loop transitions from the basal screw segment to non-screw prismatic character. The relevant kink energies are calculated using recently-developed Neural-Network Potentials (NNPs) for Mg that show good agreement versus DFT for basal and prism <a> ...

Latest version: v1
Publication date: Nov 30, 2023

Atomistic simulations reveal strength reductions due to short-range order in alloys


Xin Liu, William Curtin

  • A theory for strengthening for multicomponent non-dilute alloys possessing short-range order (SRO) has recently been developed. The theory predicts that, in addition to a well-known athermal strengthening, there is a notable effect of SRO on the solute–dislocation interactions that can decrease or increase the strength relative to a random alloy. Here, carefully designed atomistic simulations in a model binary NbW alloy are used to demonstrate that alloy strength due to solute–dislocation interactions can be increased or decreased, depending on the SRO and consistent with theoretical predictions. Specifically, SRO is introduced using fictitious solute– solute interactions in an alloy system with very small true solute–solute interactions, and the Nudged Elastic Band (NEB) method is then used to compute the energy barriers for edge dislocation motion for various levels of SRO. Energy barriers, and hence alloy strengths, can be decreased when the Warren-Cowley SRO parameters are ...

Latest version: v1
Publication date: Nov 30, 2023

Surface-symmetry-driven Dzyaloshinskii-Moriya interaction and canted ferrimagnetism in collinear magnetoelectric antiferromagnet Cr₂O₃


Oleksandr Pylypovskyi, Sophie Weber, Pavlo Makushko, Igor Veremchuk, Nicola Spaldin, Denys Makarov

  • Antiferromagnets are normally thought of as materials with compensated magnetic sublattices. This adds to their technological advantages but complicates readout of the antiferromagnetic state. We demonstrate theoretically the existence of a Dzyaloshinskii-Moriya interaction (DMI) which is determined by the magnetic symmetry classes of Cr₂O₃ surfaces with an in-plane magnetic easy axis. The DMI explains a previously predicted out-of-plane magnetization at the nominally compensated surfaces of chromia, leading to a surface-localized canted ferrimagnetism. This is in agreement with magnetotransport measurements and with density functional theory predictions which further allow us to quantify the strength of DMI. The temperature dependence of the transversal resistance for these planes shows distinct behavior in comparison with that of the Cr₂O₃ plane, which we attribute to the influence of DMI. Our work provides a framework to analyze surface-driven phenomena in antiferromagnets, ...

Latest version: v1
Publication date: Nov 29, 2023

Efficient periodic resolution-of-the-identity Hartree-Fock exchange method with k-point sampling and Gaussian basis sets


Augustin Bussy, Jürg Hutter

  • Simulations of condensed matter systems at the hybrid density functional theory (DFT) level pose significant computational challenges. The elevated costs arise from the non-local nature of the Hartree-Fock exchange (HFX) in conjunction with the necessity to approach the thermodynamic limit (TDL). In this work, we address these issues with the development of a new efficient method for the calculation of HFX in periodic systems, employing k-point sampling. We rely on a local atom-specific resolution-of-the-identity scheme, the use of atom-centered Gaussian type orbitals (GTOs), and the truncation of the Coulomb interaction to limit computational complexity. Our real-space approach exhibits a scaling that is at worst linear with the number of k-points. Issues related to basis set diffuseness are effectively addressed through the auxiliary density matrix method (ADMM). We report the implementation in the CP2K software package, as well as accuracy and performance benchmarks. The ...

Latest version: v1
Publication date: Nov 29, 2023

Machine learning-accelerated discovery of A₂BC₂ ternary electrides with diverse anionic electron densities


Zhiqi Wang, Yutong Gong, Matthew L. Evans, Yujing Yan, Shiyao Wang, Nanxi Miao, Ruiheng Zheng, Gian-Marco Rignanese, Junjie Wang

  • This study combines machine learning (ML) and high-throughput calculations to uncover new ternary electrides in the A₂BC₂ family of compounds with the P4/mbm space group. Starting from a library of 214 known A₂BC₂ phases, density-functional theory calculations were used to compute the maximum value of the electron localization function, indicating that 42 are potential electrides. A model was then trained on this dataset and used to predict the electride behaviour of 14,437 hypothetical compounds generated by structural prototyping. Then, the stability and electride features of the 1254 electride candidates predicted by the model were carefully checked by high-throughput calculations.

Latest version: v1
Publication date: Nov 28, 2023

Relaxed thin film structures of one, two, and three magnetic 3d transition metal layers on FCC noble-metal substrates based on FLAPW PBE calculations


Robin Hilgers, Daniel Wortmann, Stefan Blügel

  • The uploaded data set contains setups of all 6660 possible combinations of up to three atomic layers of 3d transition metals on six different FCC noble-metal substrates. The substrates are modelled by five layers of Ag, Au, Pd, Pt, Rh or Ir in the (001) orientation. Nearly all structures (6282) have been relaxed, i.e. their ground state atomic configuration has been determined by density functional theory calculations. This has been achieved using a workflow implemented in the AiiDA-FLEUR package that first determines the substrate lattice constant and then relaxes the interlayer distances of the ad-layers using the forces calculated. All simulations have been performed using the FLAPW code FLEUR with the standard GGA-PBE exchange-correlation functional. A significant portion of these 3d thin films exhibits magnetic properties and thus could have applications in emerging technological fields such as e.g. spintronics. Therefore, the database also includes the magnetic properties of ...

Latest version: v1
Publication date: Nov 22, 2023

Single-model uncertainty quantification in neural network potentials does not consistently outperform model ensembles


Aik Rui Tan, Shingo Urata, Samuel Goldman, Johannes C. B. Dietschreit, Rafael Gómez-Bombarelli

  • Neural networks (NNs) often assign high confidence to their predictions, even for points far out-of-distribution, making uncertainty quantification (UQ) a challenge. When they are employed to model interatomic potentials in materials systems, this problem leads to unphysical structures that disrupt simulations, or to biased statistics and dynamics that do not reflect the true physics. Differentiable UQ techniques can find new informative data and drive active learning loops for robust potentials. However, a variety of UQ techniques, including newly developed ones, exist for atomistic simulations and there are no clear guidelines for which are most effective or suitable for a given case. In this work, we examine multiple UQ schemes for improving the robustness of NN interatomic potentials (NNIPs) through active learning. In particular, we compare incumbent ensemble-based methods against strategies that use single, deterministic NNs: mean-variance estimation, deep evidential ...

Latest version: v2
Publication date: Nov 21, 2023

Dual activation and C-C coupling on single atom catalyst for CO₂ photoreduction


Fu-li Sun, Cun-biao Lin, Wei Zhang, Qing Chen, Wen-xian Chen, Xiao-nian Li, Gui-lin Zhuang

  • An excellent single-atomic photocatalyst, Ti@C₄N₃, is theoretically found to effectively convert CO₂ to C₂H₆ by density functional theory (DFT) calculations and non-adiabatic molecular dynamics (NAMD) simulations. The Ti@C₄N₃ photocatalyst has remarkable stability both thermally, chemically, and mechanically. Electronically, it has strong absorption properties, suitable band positions, and a long photogenerated electron lifetime, allowing photogenerated electrons to migrate to the surface. Notably, the high-valence active site effectively activates two CO₂ through dual activation: Under light irradiation, the weakly adsorbed CO₂ undergoes photo-induced activation by the photoelectron of conduction band minimum (CBM); without light, the high Lewis acidity of the Ti site induces CO₂ activation through back-donating π-bond. Contrast simulation results uncovered that dual activation of CO₂ is attributed to the thermal and photonic synergy. Furthermore, two activated CO₂ species under ...

Latest version: v1
Publication date: Nov 20, 2023

High-throughput computation of ab initio Raman spectra for two-dimensional materials


Geng Li, Yingxiang Gao, Daiyou Xie, Leilei Zhu, Dongjie Shi, Shuming Zeng, Wei Zhan, Jun Chen, Honghui Shang

  • Raman spectra play an important role in characterizing two-dimensional materials, as they provide a direct link between the atomic structure and the spectral features. In this work, we present an automatic computational workflow for Raman spectra using all-electron density functional perturbation theory. Utilizing this workflow, we have successfully completed the Raman spectra calculation for 3504 different two-dimensional materials, with the resultant data saved in a data repository.

Latest version: v1
Publication date: Nov 16, 2023

Automated prediction of ground state spin for transition metal complexes


Yuri Cho, Ruben Laplaza, Sergi Vela, Clemence Corminboeuf

  • Predicting the ground state spin of transition metal complexes is a challenging task. Previous attempts have been focused on specific regions of chemical space, whereas a more general automated approach is required to process crystallographic structures for high-throughput quantum chemistry computations. In this work, we developed a method to predict ground state spins of transition metal complexes. We started by constructing a dataset which contains 2,032 first row transition metal complexes taken from experimental crystal structures and their computed ground state spins. This dataset showed large chemical diversity in terms of metals, metal oxidation states, coordination geometries, and ligands. Then, we analyzed the trends between structural and electronic features of the complexes and their ground state spins, and put forward an empirical spin state assignment model. We also used simple descriptors to build a statistical model with 97% predictive accuracy across the board. ...

Latest version: v1
Publication date: Nov 15, 2023

A genetic optimization strategy with generality in asymmetric organocatalysis as primary target


Simone Gallarati, Puck van Gerwen, Ruben Laplaza, Lucien Brey, Alexander Makaveev, Clemence Corminboeuf

  • A catalyst possessing a broad substrate scope, in terms of both turnover and enantioselectivity, is sometimes called “general”. Despite their great utility in asymmetric synthesis, truly general catalysts are difficult or expensive to discover via traditional high-throughput screening and are, therefore, rare. Existing computational tools accelerate the evaluation of reaction conditions from a pre-defined set of experiments to identify the most general ones, but cannot generate entirely new catalysts with enhanced substrate breadth. For these reasons, we report an inverse design strategy based on the open-source genetic algorithm NaviCatGA and on the OSCAR database of organocatalysts to simultaneously probe the catalyst and substrate scope and optimize generality as primary target. We apply this strategy to the Pictet–Spengler condensation, for which we curate a database of 820 reactions, used to train statistical models of selectivity and activity. Starting from OSCAR, we define ...

Latest version: v2
Publication date: Nov 15, 2023

Fixed node diffusion Monte Carlo energies for over one thousand small organic molecules


Bing Huang, Anatole von Lilienfeld, Jaron Krogel, Anouar Benali

  • In the past decade, quantum diffusion Monte Carlo (DMC) has been demonstrated to successfully predict the energetics and properties of a wide range of molecules and solids by numerically solving the electronic many-body Schrödinger equation. We show that when coupled with quantum machine learning (QML) based surrogate methods the computational burden can be alleviated such that QMC shows clear potential to undergird the formation of high quality descriptions across chemical space. We discuss three crucial approximations necessary to accomplish this: The fixed node approximation, universal and accurate references for chemical bond dissociation energies, and scalable minimal amons set based QML (AQML) models. Numerical evidence presented includes converged DMC results for over one thousand small organic molecules with up to 5 heavy atoms used as amons, and 50 medium sized organic molecules with 9 heavy atoms to validate the AQML predictions. Numerical evidence collected for 𝛥-AQML ...

Latest version: v2
Publication date: Nov 15, 2023

Experimental and ab initio derivation of interface stress in nanomultilayered coatings: application to immiscible Cu/W system with variable in-plane stress


Giacomo Lorenzin, Javier Fernandez Troncoso, Manura Liyanage, Aleksandr Druzhinin, Lars Jeurgens, Claudia Cancellieri, Vladyslav Turlo

  • Interface stress is a fundamental descriptor for interphase boundaries and is defined in strict relation to the interface energy. In nanomultilayered coatings with their intrinsically high interface density, the functional properties are generally dictated by the interface structure, which in turn is governed by the delicate interaction of residual interface and volume stresses in the coating system. In the present work, experimental estimations of the interface stress in Cu/W NMLs (with a variable residual stress state from tensile to compressive) were compared with corresponding theoretical values as calculated using DFT (adopting an incoherent bcc W{110}/fcc Cu{111} interface with variable in-plane strain). The Cu/W interface stress was experimentally tuned monotonically from positive to negative values by changing the residual stress in the W nanolayers by increasing the Ar pressure during the W deposition steps. Qualitative agreement between experiment and simulation was ...

Latest version: v1
Publication date: Nov 14, 2023

The optimal resolution level of a protein is an emergent property of its structure and dynamics


Raffaele Fiorentini, Thomas Tarenzi, Giovanni Mattiotti, Raffaello Potestio

  • Molecular dynamics simulations provide a wealth of data whose in-depth analysis can be computationally demanding and, sometimes, even unnecessary. Dimensionality reduction techniques are thus routinely employed to simplify and improve the interpretation of trajectories focusing on specific subsets of the system's atoms; a key issue, in this context, is to determine the optimal resolution level, i.e. the smallest number of atoms needed to preserve the largest information content from the full atomistic trajectory. Here, we introduce the protein optimal resolution identification method (PROPRE), an unsupervised approach built on information theory principles that determines the smallest number of atoms that need to be retained to attain a synthetic yet informative description of a protein. By applying the method to a protein dataset and two particular case studies, we show that this number is typically between 1.5 and 2 times the number of residues in a protein; nonetheless, the ...

Latest version: v1
Publication date: Nov 13, 2023

On the sign of the linear magnetoelectric coefficient in Cr₂O₃


Eric Bousquet, Eddy Lelièvre-Berna, Navid Qureshi, Jian-Rui Soh, Nicola Ann Spaldin, Andrea Urru, Xanthe Henderike Verbeek, Sophie Francis Weber

  • We establish the sign of the linear magnetoelectric (ME) coefficient, α, in chromia, Cr₂O₃. Cr₂O₃ is the prototypical linear ME material, in which an electric (magnetic) field induces a linearly proportional magnetization (polarization), and a single magnetic domain can be selected by annealing in combined magnetic (H) and electric (E) fields. Opposite antiferromagnetic domains have opposite ME responses, and which antiferromagnetic domain corresponds to which sign of response has previously been unclear. We use density functional theory (DFT) to calculate the magnetic response of a single antiferromagnetic domain of Cr₂O₃ to an applied in-plane electric field at 0 K. We find that the domain with nearest neighbor magnetic moments oriented away from (towards) each other has a negative (positive) in-plane ME coefficient, α⊥, at 0 K. We show that this sign is consistent with all other DFT calculations in the literature that specified the domain orientation, independent of the choice ...

Latest version: v1
Publication date: Nov 13, 2023

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