Direct, mediated and delayed intramolecular singlet fission mechanism in donor-acceptor copolymers

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{
  "metadata": {
    "is_last": true, 
    "version": 1, 
    "title": "Direct, mediated and delayed intramolecular singlet fission mechanism in donor-acceptor copolymers", 
    "keywords": [
      "Singlet Fission", 
      "Donor-Acceptor Copolymers", 
      "LVC model", 
      "Quantum dynamics", 
      "EPFL"
    ], 
    "description": "Donor-acceptor (D-A) extended copolymers have shown great potential to be exploited for intramolecular Singlet Fission (iSF) because of their modular tunability and intrinsic ability to incorporate low-lying charge-transfer (CT) and a triplet-pair (TT) state. While the SF mechanism has been widely debated in homo- and hetero-dimers, little is known about the singlet splitting process in A-D-A copolymer trimers. Unlike traditional two-sites SF, the process of iSF in D-A copolymers involves three molecular units consisting of two A and one D following a A-D-A polymeric chain. This scenario is therefore, different from the homo-dimer analogous in terms of which states (if any) may drive the SF process. In this work, we identify how singlet splitting occurs in prototypical iSF D-A copolymer poly(benzodithiophene-alt-thiophene-1,1-dioxide) (BDT\u2212TDO) by means of wave-packet propagations on the basis of the Linear Vibronic Coupling (LVC) model Hamiltonian. Our results reveal that three different mechanisms drive the S\u2192TT population transfer via antisymmetric and symmetric vibrational motion, including two favorable mechanisms of direct and mediated interactions, as well as a parasitic decay pathway that potentially delays the process. Remarkably, we uncover the interplay between an upper state of marked multi-excitonic character and a low-lying CT state in balancing the splitting efficiency, which anticipates their major role in defining future guidelines for the molecular design of D-A copolymers for iSF.", 
    "license": "Creative Commons Attribution 4.0 International", 
    "references": [
      {
        "url": "https://pubs.acs.org/doi/10.1021/acs.jpclett.0c03076", 
        "type": "Journal reference", 
        "citation": "M. Fumanal, C. Corminboeuf, J. Phys. Chem. Lett. (2020) 11, 9788-9794", 
        "comment": "Paper where the data is discussed", 
        "doi": "10.1021/acs.jpclett.0c03076"
      }
    ], 
    "doi": "10.24435/materialscloud:ry-hg", 
    "conceptrecid": "619", 
    "publication_date": "Nov 05, 2020, 18:19:12", 
    "edited_by": 100, 
    "_oai": {
      "id": "oai:materialscloud.org:620"
    }, 
    "contributors": [
      {
        "affiliations": [
          "Laboratory for Computational Molecular Design, Institute of Chemical Sciences and Engineering, E\u0301cole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland"
        ], 
        "email": "maria.fumanal@epfl.ch", 
        "familyname": "Fumanal", 
        "givennames": "Maria"
      }, 
      {
        "affiliations": [
          "Laboratory for Computational Molecular Design, Institute of Chemical Sciences and Engineering, E\u0301cole Polytechnique F\u00e9d\u00e9rale de Lausanne (EPFL), CH-1015 Lausanne, Switzerland"
        ], 
        "email": "clemence.corminboeuf@epfl.ch", 
        "familyname": "Corminboeuf", 
        "givennames": "Cl\u00e9mence"
      }
    ], 
    "owner": 32, 
    "license_addendum": null, 
    "mcid": "2020.140", 
    "_files": [
      {
        "size": 2281, 
        "checksum": "md5:b875ebc08ae78a87146a302e2c85c32d", 
        "description": "Readme file with the information of the database folder", 
        "key": "README.txt"
      }, 
      {
        "size": 1199694099, 
        "checksum": "md5:b114c38686f17825e49b850297326e4c", 
        "description": "The compressed folder contains all the computations reported in the paper", 
        "key": "database.tar.gz"
      }
    ], 
    "id": "620", 
    "status": "published"
  }, 
  "revision": 3, 
  "updated": "2020-11-05T17:19:12.641488+00:00", 
  "created": "2020-10-28T10:13:03.395570+00:00", 
  "id": "620"
}