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  4. Simulating Molecular Single Vibronic Level Fluorescence Spectra with Ab Initio Hagedorn Wavepacket Dynamics
 
research article

Simulating Molecular Single Vibronic Level Fluorescence Spectra with Ab Initio Hagedorn Wavepacket Dynamics

Zhang, Zhan Tong  
•
Vaníček, Jiří J. L.
September 15, 2025
Journal of Chemical Theory and Computation

We present a practical, ab initio time-dependent method using Hagedorn wavepackets to efficiently simulate single vibronic level (SVL) fluorescence spectra of polyatomic molecules from arbitrary initial vibrational levels. We apply the method to compute SVL spectra of anthracene by performing wavepacket dynamics on a 66-dimensional harmonic potential energy surface constructed from density functional theory calculations. The Hagedorn approach captures both mode distortion (frequency changes) and mode mixing (Duschinsky rotation) within the harmonic approximation. We not only reproduce the previously reported simulation results for singly excited 121 and 1̅1̅1 levels but are also able to compute SVL spectra from multiply excited levels in good agreement with experiments. Notably, all spectra were obtained from the same wavepacket trajectory without any additional propagation beyond what is required for the emission spectrum from the ground vibrational level of the electronically excited state.

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Type
research article
DOI
10.1021/acs.jctc.5c01097
Author(s)
Zhang, Zhan Tong  

École Polytechnique Fédérale de Lausanne

Vaníček, Jiří J. L.

École Polytechnique Fédérale de Lausanne

Date Issued

2025-09-15

Publisher

American Chemical Society (ACS)

Published in
Journal of Chemical Theory and Computation
Article Number

acs.jctc.5c01097

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LCPT  
FunderFunding(s)Grant NumberGrant URL

?cole Polytechnique F?d?rale de Lausanne

Available on Infoscience
September 19, 2025
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/254095
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