On-The-Fly Dynamics of Multiconfigurational Wave Packets by a Semiclassical Method.

An on-the-fly, trajectory-based semiclassical scheme for the time propagation of multiconfigurational nuclear wave packets (MCWPs) is proposed. This enables MCWP time propagation without a prefitted global potential energy surface, in contrast to variational approaches such as the widely used multiconfiguration time-dependent Hartree (MCTDH), while retaining multimode couplings and favorable scaling. Comparisons with the matrix-product-state MCTDH method for formaldehyde, together with on-the-fly infrared spectra of benzene benchmarked against experiment, show that accurate wave packet propagation can be achieved within a semiclassical framework. The approach also extends to transitions between electronic states; for benzene fluorescence, incorporating Herzberg-Teller coupling reproduces the characteristic vibronic structure.

• Publication year

  2025

• Venue

  Journal of Chemical Theory and Computation

• Publication date

  2025-11-11

• Fields of study

  Medicine, Physics, Chemistry

• Identifiers
  DOI 10.1021/acs.jctc.5c01444PMID 41220076
• 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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