000255096 001__ 255096
000255096 005__ 20190507143840.0
000255096 0247_ $$a10.1021/acs.jpclett.8b00827$$2doi
000255096 02470 $$2DOI$$a10.1021/acs.jpclett.8b00827
000255096 037__ $$aARTICLE
000255096 245__ $$aOn-the-Fly Ab Initio Semiclassical Evaluation of Absorption Spectra of Polyatomic Molecules beyond the Condon Approximation
000255096 260__ $$c2018
000255096 269__ $$a2018
000255096 336__ $$aJournal Articles
000255096 520__ $$aTo evaluate vibronic spectra beyond the Condon approximation, we extend the on-the-fly ab initio thawed Gaussian approximation by considering the Herzberg–Teller contribution due to the dependence of the electronic transition dipole moment on nuclear coordinates. The extended thawed Gaussian approximation is tested on electronic absorption spectra of the phenyl radical and benzene; calculated spectra reproduce experimental data and are much more accurate than standard global harmonic approaches, confirming the significance of anharmonicity. Moreover, the extended method provides a tool to quantify the Herzberg–Teller contribution; we show that in the phenyl radical, anharmonicity outweighs the Herzberg–Teller contribution, whereas in benzene, the Herzberg–Teller contribution is essential because the transition is electronically forbidden and the Condon approximation yields a zero spectrum. Surprisingly, both adiabatic harmonic spectra outperform those of the vertical harmonic model, which describes the Franck–Condon region better. Finally, we provide a simple recipe for orientationally averaging spectra, valid beyond the Condon approximation, and a relation among the transition dipole, its gradient, and nonadiabatic coupling vectors.
000255096 536__ $$aH2020$$c683069
000255096 536__ $$aFNS-NCCR$$cMUST
000255096 6531_ $$aOn-the-fly ab initio methods
000255096 6531_ $$aSemiclassical dynamics
000255096 6531_ $$aHerzberg--Teller approximation
000255096 6531_ $$aAbsorption spectra
000255096 700__ $$g186112$$0247604$$aPatoz, Aurélien
000255096 700__ $$aBegušić, Tomislav
000255096 700__ $$aVaníček, Jiří
000255096 773__ $$q2367-2372$$j9$$tThe Journal of Physical Chemistry Letters
000255096 790__ $$w10.1021/acs.jpclett.8b00827$$2doi
000255096 8560_ $$fnikolay.golubev@epfl.ch
000255096 8564_ $$uhttps://infoscience.epfl.ch/record/255096/files/acs.jpclett.8b00827.pdf$$zFinal$$s971003
000255096 909C0 $$mjiri.vanicek@epfl.ch$$zBorel, Alain$$pLCPT$$xU11812$$0252116
000255096 909CO $$qGLOBAL_SET$$pSB$$particle$$ooai:infoscience.epfl.ch:255096
000255096 960__ $$asergey.antipov@epfl.ch
000255096 961__ $$alaurence.gauvin@epfl.ch
000255096 973__ $$aEPFL$$sPUBLISHED$$rREVIEWED
000255096 980__ $$aARTICLE
000255096 981__ $$aoverwrite