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  4. On-the-Fly Ab Initio Semiclassical Evaluation of Absorption Spectra of Polyatomic Molecules beyond the Condon Approximation
 
research article

On-the-Fly Ab Initio Semiclassical Evaluation of Absorption Spectra of Polyatomic Molecules beyond the Condon Approximation

Patoz, Aurélien  
•
Begušić, Tomislav
•
Vaníček, Jiří
2018
The Journal of Physical Chemistry Letters

To 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.

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Type
research article
DOI
10.1021/acs.jpclett.8b00827
Author(s)
Patoz, Aurélien  
Begušić, Tomislav
Vaníček, Jiří
Date Issued

2018

Published in
The Journal of Physical Chemistry Letters
Volume

9

Start page

2367

End page

2372

Subjects

On-the-fly ab initio methods

•

Semiclassical dynamics

•

Herzberg--Teller approximation

•

Absorption spectra

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCPT  
FunderGrant Number

H2020

683069

FNS-NCCR

MUST

RelationURL/DOI

IsSupplementedBy

https://doi.org/10.1021/acs.jpclett.8b00827
Available on Infoscience
April 25, 2018
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/146187
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