Structural diradical character
© 2018 Wiley Periodicals, Inc.
| Publié dans: | Journal of computational chemistry. - 1984. - 40(2019), 7 vom: 15. März, Seite 854-865 |
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| Auteur principal: | |
| Autres auteurs: | , |
| Format: | Article en ligne |
| Langue: | English |
| Publié: |
2019
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| Accès à la collection: | Journal of computational chemistry |
| Sujets: | Journal Article bond length alternation density functional theory diradical character molecular structure open-shell singlet |
| Résumé: | © 2018 Wiley Periodicals, Inc. A reliable first-principles description of singlet diradical character is essential for predicting nonlinear optical and magnetic properties of molecules. As diradical and closed-shell electronic structures differ in their distribution of single, double, triple, and aromatic bonds, modeling electronic diradical character requires accurate bond-length patterns, in addition to accurate absolute bond lengths. We therefore introduce structural diradical character, which we suggest as an additional measure for comparing first-principles calculations with experimental data. We employ this measure to identify suitable exchange-correlation functionals for predicting the bond length patterns and electronic diradical character of a biscobaltocene with the potential for photoswitchable nonlinear optical activity. Out of four popular approximate exchange-correlation functionals with different exact-exchange admixtures (BP86, TPSS, B3LYP, TPSSh), the two hybrid functionals TPSSh and B3LYP perform best for diradical bond length patterns, with TPSSh being best for the organometallic validation systems and B3LYP for the organic ones (for which the D3 dispersion correction was included). Still, none of the functionals is suitable for correctly describing relative bond lengths across the range of molecules studied, so that none can be recommended for predictive studies of (potential) diradicals without reservation. © 2018 Wiley Periodicals, Inc |
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| Description: | Date Revised 20.11.2019 published: Print-Electronic Citation Status PubMed-not-MEDLINE |
| ISSN: | 1096-987X |
| DOI: | 10.1002/jcc.25768 |