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

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.

• Publication year

  2024

• Venue

  Journal of Chemical Theory and Computation

• Publication date

  2024-03-01

• Fields of study

  Medicine, Physics, Chemistry

• Identifiers
  DOI 10.1021/acs.jctc.5c01097arXiv 2403.00702PMID 40953496PMCID 12529895
• External record

  Open on Semantic Scholar

• Source metadata

  Semantic Scholar, PubMed

• No claims are published for this paper.

• No concepts are published for this paper.

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• A New Expression for Multidimensional Franck-Condon Integrals.

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• Exponentially Accurate Semiclassical Dynamics: Propagation, Localization, Ehrenfest Times, Scattering, and More General States

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• Dynamics of intramolecular vibrational‐energy redistribution (IVR). II. Excess energy dependence

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  1982cited by this paper
• A discussion of the solution for the best rotation to relate two sets of vectors

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• Classical S‐matrix limit of wave packet dynamics

  1976cited by this paper
• Time‐dependent approach to semiclassical dynamics

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• Resonance fluorescence of aniline vapour

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• Some Studies Concerning Rotating Axes and Polyatomic Molecules

  1935cited by this paper

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