Efficient Semiclassical Evaluation of Electronic Coherences in Polyatomic Molecules

Authors

  • Nikolay Golubev Laboratory of Theoretical Physical Chemistry, Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Av. F.-A. Forel 2, CH-1015 Lausanne
  • Jiří Vaníček Laboratory of Theoretical Physical Chemistry, Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique Fédérale de Lausanne (EPFL), Av. F.-A. Forel 2, CH-1015 Lausanne

DOI:

https://doi.org/10.2533/chimia.2022.575

Keywords:

Electron-nuclear couplings, First-principles calculations, Semiclassical methods, Ultrafast electron dynamics

Abstract

Exposing a molecule to intense light pulses may bring this molecule to a nonstationary quantum state, thus launching correlated dynamics of electronic and nuclear subsystems. Although much had been achieved in the understanding of fundamental physics behind the electron-nuclear interactions and dynamics, accurate numerical simulations of light-induced processes taking place in polyatomic molecules remain a formidable challenge. Here, we review a recently developed theoretical approach for evaluating electronic coherences in molecules, in which the ultrafast electronic dynamics is coupled to nuclear motion. The presented technique, which combines accurate ab initio on-the-fly simulations of electronic structure with efficient semiclassical procedure to compute the dynamics of nuclear wave packets, is not only computationally efficient, but also can help shed light on the underlying physical mechanisms of decoherence and revival of the electronic coherences driven by nuclear rearrangement.

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Published

2022-06-29

How to Cite

[1]
N. Golubev, J. Vaníček, Chimia 2022, 76, 575, DOI: 10.2533/chimia.2022.575.