{"title":"激发能量传递中的分子内振动:来自实时路径积分计算的见解。","authors":"Sohang Kundu, Nancy Makri","doi":"10.1146/annurev-physchem-090419-120202","DOIUrl":null,"url":null,"abstract":"<p><p>Excitation energy transfer (EET) is fundamental to many processes in chemical and biological systems and carries significant implications for the design of materials suitable for efficient solar energy harvest and transport. This review discusses the role of intramolecular vibrations on the dynamics of EET in nonbonded molecular aggregates of bacteriochlorophyll, a perylene bisimide, and a model system, based on insights obtained from fully quantum mechanical real-time path integral results for a Frenkel exciton Hamiltonian that includes all vibrational modes of each molecular unit at finite temperature. Generic trends, as well as features specific to the vibrational characteristics of the molecules, are identified. Weak exciton-vibration (EV) interaction leads to compact, near-Gaussian densities on each electronic state, whose peak follows primarily a classical trajectory on a torus, while noncompact densities and nonlinear peak evolution are observed with strong EV coupling. Interaction with many intramolecular modes and increasing aggregate size smear, shift, and damp these dynamical features.</p>","PeriodicalId":7967,"journal":{"name":"Annual review of physical chemistry","volume":null,"pages":null},"PeriodicalIF":11.7000,"publicationDate":"2022-04-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"23","resultStr":"{\"title\":\"Intramolecular Vibrations in Excitation Energy Transfer: Insights from Real-Time Path Integral Calculations.\",\"authors\":\"Sohang Kundu, Nancy Makri\",\"doi\":\"10.1146/annurev-physchem-090419-120202\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Excitation energy transfer (EET) is fundamental to many processes in chemical and biological systems and carries significant implications for the design of materials suitable for efficient solar energy harvest and transport. This review discusses the role of intramolecular vibrations on the dynamics of EET in nonbonded molecular aggregates of bacteriochlorophyll, a perylene bisimide, and a model system, based on insights obtained from fully quantum mechanical real-time path integral results for a Frenkel exciton Hamiltonian that includes all vibrational modes of each molecular unit at finite temperature. Generic trends, as well as features specific to the vibrational characteristics of the molecules, are identified. Weak exciton-vibration (EV) interaction leads to compact, near-Gaussian densities on each electronic state, whose peak follows primarily a classical trajectory on a torus, while noncompact densities and nonlinear peak evolution are observed with strong EV coupling. Interaction with many intramolecular modes and increasing aggregate size smear, shift, and damp these dynamical features.</p>\",\"PeriodicalId\":7967,\"journal\":{\"name\":\"Annual review of physical chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":11.7000,\"publicationDate\":\"2022-04-20\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"23\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Annual review of physical chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1146/annurev-physchem-090419-120202\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2022/1/26 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Annual review of physical chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1146/annurev-physchem-090419-120202","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2022/1/26 0:00:00","PubModel":"Epub","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Intramolecular Vibrations in Excitation Energy Transfer: Insights from Real-Time Path Integral Calculations.
Excitation energy transfer (EET) is fundamental to many processes in chemical and biological systems and carries significant implications for the design of materials suitable for efficient solar energy harvest and transport. This review discusses the role of intramolecular vibrations on the dynamics of EET in nonbonded molecular aggregates of bacteriochlorophyll, a perylene bisimide, and a model system, based on insights obtained from fully quantum mechanical real-time path integral results for a Frenkel exciton Hamiltonian that includes all vibrational modes of each molecular unit at finite temperature. Generic trends, as well as features specific to the vibrational characteristics of the molecules, are identified. Weak exciton-vibration (EV) interaction leads to compact, near-Gaussian densities on each electronic state, whose peak follows primarily a classical trajectory on a torus, while noncompact densities and nonlinear peak evolution are observed with strong EV coupling. Interaction with many intramolecular modes and increasing aggregate size smear, shift, and damp these dynamical features.
期刊介绍:
The Annual Review of Physical Chemistry has been published since 1950 and is a comprehensive resource for significant advancements in the field. It encompasses various sub-disciplines such as biophysical chemistry, chemical kinetics, colloids, electrochemistry, geochemistry and cosmochemistry, chemistry of the atmosphere and climate, laser chemistry and ultrafast processes, the liquid state, magnetic resonance, physical organic chemistry, polymers and macromolecules, and others.