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Radicals in aqueous solution: Assessment of density-corrected SCAN functional

Fabian Belleflamme1*, Juerg Hutter1*

1 Department of Chemistry, University of Zurich (UZH), CH-8057 Zurich, Zurich, Switzerland

* Corresponding authors emails: fabian.belleflamme@chem.uzh.ch, hutter@chem.uzh.ch
DOI10.24435/materialscloud:y4-7s [version v1]

Publication date: May 31, 2023

How to cite this record

Fabian Belleflamme, Juerg Hutter, Radicals in aqueous solution: Assessment of density-corrected SCAN functional, Materials Cloud Archive 2023.85 (2023), https://doi.org/10.24435/materialscloud:y4-7s

Description

We study self-interaction effects in solvated and strongly-correlated cationic molecular clusters, with a focus on the solvated hydroxyl radical. To address the self-interaction issue, we apply the DC-r²SCAN method, with the auxiliary density matrix approach. Validating our method through simulations of bulk liquid water, we demonstrate that DC-r²SCAN maintains the structural accuracy of r²SCAN while effectively addressing spin density localization issues. Extending our analysis to solvated cationic molecular clusters, we find that the hemibonded motif in the [CH₃S∴CH₃SH]⁺ cluster is disrupted in the DC-r²SCAN simulation, in contrast to r²SCAN that preserves the (three-electron-two-center)-bonded motif. Similarly, for the [SH∴SH₂]⁺ cluster, r²SCAN restores the hemibonded motif through spin leakage, while DC-r²SCAN predicts a weaker hemibond formation influenced by solvent-solute interactions. Our findings demonstrate the potential of DC-r²SCAN combined with the auxiliary density matrix method to improve electronic structure calculations, providing insights into the properties of solvated cationic molecular clusters. This work contributes to the advancement of self-interaction corrected electronic structure theory and offers a computational framework for modeling condensed phase systems with intricate correlation effects.

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Files

File name Size Description
OHradical.tar.gz
MD5md5:36dcd11def7cdff7d23ffce7015065a3
1.5 GiB Hydroxyl radical solvated in 63 water molecules. Provided are input files for CP2K, and 30ps trajectories generated from this input.
SHradical.tar.gz
MD5md5:4b6c65972b84b9b99359d28043b86621
1.5 GiB Sulfanyl radical solvated in 63 water molecules. Provided are input files for CP2K, and 30ps trajectories generated from this input.
CH3S_CH3SH.tar.gz
MD5md5:b61b72ec1ac1adc5bc1a667ca498539a
1.5 GiB Radical cation cluster [CH₃S∴CH₃SH]⁺ solvated in 64 water molecules. Provided are input files for CP2K, and 30ps trajectories generated from this input.
HS_SH2.tar.gz
MD5md5:025520107d4777e44becfc770a7fbacc
1.4 GiB Radical cation cluster [SH∴SH₂]⁺ solvated in 62 water molecules. Provided are input files for CP2K, and 30ps trajectories generated from this input.
H2O.tar.gz
MD5md5:1257fc80410f5129854b660c65b54fe2
1.0 GiB Bulk liquid water of 64 molecules. Provided are input files for CP2K, and 30ps trajectories generated from this input.

License

Files and data are licensed under the terms of the following license: Creative Commons Attribution 4.0 International.
Metadata, except for email addresses, are licensed under the Creative Commons Attribution Share-Alike 4.0 International license.

External references

Journal reference (Submitted manuscript where the data is discussed)
F. Belleflamme, J. Hutter, PCCP, (2023) (submitted)

Keywords

Density-corrected DFT Density functional theory r2SCAN Aqueous hydroxyl radical Aqueous sulfanyl radical Methanethiol Hydrogen sulfide

Version history:

2023.85 (version v1) [This version] May 31, 2023 DOI10.24435/materialscloud:y4-7s