{"title":"控制电子一致性和锥形交叉点衍生耦合引起的曲率:应用于 \"通道 3 \"苯光化学的量子艾伦费斯特(QuEh)反应路径跟踪协议。","authors":"Graham A. Worth, and , Michael A. Robb*, ","doi":"10.1021/acs.jpca.4c02449","DOIUrl":null,"url":null,"abstract":"<p >We report a protocol for the implementation of “reaction path following” from a transition state through a conical intersection, including both the path curvature induced by the derivative coupling and the corresponding induced electronic coherences. This protocol focuses on the “central” Gaussian wavepacket (initially unexcited) in the quantum Ehrenfest (QuEh) method. Like the reaction path following, the normal mode corresponding to the imaginary frequency at the transition state is given an initial momentum. The protocol is applied to the “channel 3” radiationless decay of benzene. We also demonstrate that one can enhance the effect of the derivative coupling and the electronic coherence with an IR pulse.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":null,"pages":null},"PeriodicalIF":2.7000,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acs.jpca.4c02449","citationCount":"0","resultStr":"{\"title\":\"Controlling Electronic Coherences and the Curvature Induced by the Derivative Coupling at a Conical Intersection: A Quantum Ehrenfest (QuEh) Protocol for Reaction Path Following Application to “Channel 3” Benzene Photochemistry\",\"authors\":\"Graham A. Worth, and , Michael A. Robb*, \",\"doi\":\"10.1021/acs.jpca.4c02449\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >We report a protocol for the implementation of “reaction path following” from a transition state through a conical intersection, including both the path curvature induced by the derivative coupling and the corresponding induced electronic coherences. This protocol focuses on the “central” Gaussian wavepacket (initially unexcited) in the quantum Ehrenfest (QuEh) method. Like the reaction path following, the normal mode corresponding to the imaginary frequency at the transition state is given an initial momentum. The protocol is applied to the “channel 3” radiationless decay of benzene. We also demonstrate that one can enhance the effect of the derivative coupling and the electronic coherence with an IR pulse.</p>\",\"PeriodicalId\":59,\"journal\":{\"name\":\"The Journal of Physical Chemistry A\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.7000,\"publicationDate\":\"2024-06-25\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/epdf/10.1021/acs.jpca.4c02449\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry A\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.jpca.4c02449\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry A","FirstCategoryId":"1","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.jpca.4c02449","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Controlling Electronic Coherences and the Curvature Induced by the Derivative Coupling at a Conical Intersection: A Quantum Ehrenfest (QuEh) Protocol for Reaction Path Following Application to “Channel 3” Benzene Photochemistry
We report a protocol for the implementation of “reaction path following” from a transition state through a conical intersection, including both the path curvature induced by the derivative coupling and the corresponding induced electronic coherences. This protocol focuses on the “central” Gaussian wavepacket (initially unexcited) in the quantum Ehrenfest (QuEh) method. Like the reaction path following, the normal mode corresponding to the imaginary frequency at the transition state is given an initial momentum. The protocol is applied to the “channel 3” radiationless decay of benzene. We also demonstrate that one can enhance the effect of the derivative coupling and the electronic coherence with an IR pulse.
期刊介绍:
The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.