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Multistate Energy Decomposition Analysis of Molecular Excited States

[Image: see text] A multistate energy decomposition analysis (MS-EDA) method is described to dissect the energy components in molecular complexes in excited states. In MS-EDA, the total binding energy of an excimer or an exciplex is partitioned into a ground-state term, called local interaction ener...

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Autores principales: Hettich, Christian P., Zhang, Xiaoyong, Kemper, David, Zhao, Ruoqi, Zhou, Shaoyuan, Lu, Yangyi, Gao, Jiali, Zhang, Jun, Liu, Meiyi
Formato: Online Artículo Texto
Lenguaje:English
Publicado: American Chemical Society 2023
Acceso en línea:https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10369419/
https://www.ncbi.nlm.nih.gov/pubmed/37502166
http://dx.doi.org/10.1021/jacsau.3c00186
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author Hettich, Christian P.
Zhang, Xiaoyong
Kemper, David
Zhao, Ruoqi
Zhou, Shaoyuan
Lu, Yangyi
Gao, Jiali
Zhang, Jun
Liu, Meiyi
author_facet Hettich, Christian P.
Zhang, Xiaoyong
Kemper, David
Zhao, Ruoqi
Zhou, Shaoyuan
Lu, Yangyi
Gao, Jiali
Zhang, Jun
Liu, Meiyi
author_sort Hettich, Christian P.
collection PubMed
description [Image: see text] A multistate energy decomposition analysis (MS-EDA) method is described to dissect the energy components in molecular complexes in excited states. In MS-EDA, the total binding energy of an excimer or an exciplex is partitioned into a ground-state term, called local interaction energy, and excited-state contributions that include exciton excitation energy, superexchange stabilization, and orbital and configuration-state delocalization. An important feature of MS-EDA is that key intermediate states associated with different energy terms can be variationally optimized, providing quantitative insights into widely used physical concepts such as exciton delocalization and superexchange charge-transfer effects in excited states. By introducing structure-weighted adiabatic excitation energy as the minimum photoexcitation energy needed to produce an excited-state complex, the binding energy of an exciplex and excimer can be defined. On the basis of the nature of intermolecular forces through MS-EDA analysis, it was found that molecular complexes in the excited states can be classified into three main categories, including (1) encounter excited-state complex, (2) charge-transfer exciplex, and (3) intimate excimer or exciplex. The illustrative examples in this Perspective highlight the interplay of local excitation polarization, exciton resonance, and superexchange effects in molecular excited states. It is hoped that MS-EDA can be a useful tool for understanding photochemical and photobiological processes.
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spelling pubmed-103694192023-07-27 Multistate Energy Decomposition Analysis of Molecular Excited States Hettich, Christian P. Zhang, Xiaoyong Kemper, David Zhao, Ruoqi Zhou, Shaoyuan Lu, Yangyi Gao, Jiali Zhang, Jun Liu, Meiyi JACS Au [Image: see text] A multistate energy decomposition analysis (MS-EDA) method is described to dissect the energy components in molecular complexes in excited states. In MS-EDA, the total binding energy of an excimer or an exciplex is partitioned into a ground-state term, called local interaction energy, and excited-state contributions that include exciton excitation energy, superexchange stabilization, and orbital and configuration-state delocalization. An important feature of MS-EDA is that key intermediate states associated with different energy terms can be variationally optimized, providing quantitative insights into widely used physical concepts such as exciton delocalization and superexchange charge-transfer effects in excited states. By introducing structure-weighted adiabatic excitation energy as the minimum photoexcitation energy needed to produce an excited-state complex, the binding energy of an exciplex and excimer can be defined. On the basis of the nature of intermolecular forces through MS-EDA analysis, it was found that molecular complexes in the excited states can be classified into three main categories, including (1) encounter excited-state complex, (2) charge-transfer exciplex, and (3) intimate excimer or exciplex. The illustrative examples in this Perspective highlight the interplay of local excitation polarization, exciton resonance, and superexchange effects in molecular excited states. It is hoped that MS-EDA can be a useful tool for understanding photochemical and photobiological processes. American Chemical Society 2023-06-24 /pmc/articles/PMC10369419/ /pubmed/37502166 http://dx.doi.org/10.1021/jacsau.3c00186 Text en © 2023 The Authors. Published by American Chemical Society https://creativecommons.org/licenses/by-nc-nd/4.0/Permits non-commercial access and re-use, provided that author attribution and integrity are maintained; but does not permit creation of adaptations or other derivative works (https://creativecommons.org/licenses/by-nc-nd/4.0/).
spellingShingle Hettich, Christian P.
Zhang, Xiaoyong
Kemper, David
Zhao, Ruoqi
Zhou, Shaoyuan
Lu, Yangyi
Gao, Jiali
Zhang, Jun
Liu, Meiyi
Multistate Energy Decomposition Analysis of Molecular Excited States
title Multistate Energy Decomposition Analysis of Molecular Excited States
title_full Multistate Energy Decomposition Analysis of Molecular Excited States
title_fullStr Multistate Energy Decomposition Analysis of Molecular Excited States
title_full_unstemmed Multistate Energy Decomposition Analysis of Molecular Excited States
title_short Multistate Energy Decomposition Analysis of Molecular Excited States
title_sort multistate energy decomposition analysis of molecular excited states
url https://www.ncbi.nlm.nih.gov/pmc/articles/PMC10369419/
https://www.ncbi.nlm.nih.gov/pubmed/37502166
http://dx.doi.org/10.1021/jacsau.3c00186
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