Analysis of Localized Diabatic States beyond the Condon Approximation for Excitation Energy Transfer Processes
| العنوان: | Analysis of Localized Diabatic States beyond the Condon Approximation for Excitation Energy Transfer Processes |
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| المؤلفون: | Yihan Shao, Shervin Fatehi, Ethan Alguire, Joseph E. Subotnik |
| المصدر: | The Journal of Physical Chemistry A. 118:11891-11900 |
| بيانات النشر: | American Chemical Society (ACS), 2014. |
| سنة النشر: | 2014 |
| مصطلحات موضوعية: | chemistry.chemical_compound, chemistry, Quantum mechanics, Energy transfer, Diabatic, Molecule, Physical and Theoretical Chemistry, Chemical reaction, Derivative (chemistry), Excitation |
| الوصف: | In a previous paper [Fatehi, S.; et al. J. Chem. Phys. 2013, 139, 124112], we demonstrated a practical method by which analytic derivative couplings of Boys-localized CIS states can be obtained. In this paper, we now apply that same method to the analysis of triplet–triplet energy transfer systems studied by Closs and collaborators [Closs, G. L.; et al. J. Am. Chem. Soc. 1988, 110, 2652]. For the systems examined, we are able to conclude that (i) the derivative coupling in the BoysOV basis is negligible, and (ii) the diabatic coupling will likely change little over the configuration space explored at room temperature. Furthermore, we propose and evaluate an approximation that allows for the inexpensive calculation of accurate diabatic energy gradients, called the "strictly diabatic" approximation. This work highlights the effectiveness of diabatic state analytic gradient theory in realistic systems and demonstrates that localized diabatic states can serve as an acceptable approximation to strictly diabatic states. This document is the unedited Author's version of a Submitted Work that was subsequently accepted for publication in The Journal of Physical Chemistry A, copyright © American Chemical Society after peer review. To access the final edited and published work see http://pubs.acs.org/articlesonrequest/AOR-HIycfcJ6ckzbNcRqfKPN. |
| تدمد: | 1520-5215 1089-5639 |
| URL الوصول: | https://explore.openaire.eu/search/publication?articleId=doi_dedup___::3b9d7423867f8ecceb98a553dbad0461 https://doi.org/10.1021/jp411107k |
| حقوق: | OPEN |
| رقم الأكسشن: | edsair.doi.dedup.....3b9d7423867f8ecceb98a553dbad0461 |
| قاعدة البيانات: | OpenAIRE |
Find this issue from the American Chemical Society | تدمد: | 15205215 10895639 |
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