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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...
Autores principales: | , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical Society
2023
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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. |
format | Online Article Text |
id | pubmed-10369419 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2023 |
publisher | American Chemical Society |
record_format | MEDLINE/PubMed |
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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