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Exact factorization of the photon–electron–nuclear wavefunction: Formulation and coupled-trajectory dynamics.

Authors :
Sangiogo Gil, Eduarda
Lauvergnat, David
Agostini, Federica
Source :
Journal of Chemical Physics. 8/28/2024, Vol. 161 Issue 8, p1-19. 19p.
Publication Year :
2024

Abstract

We employ the exact-factorization formalism to study the coupled dynamics of photons, electrons, and nuclei at the quantum mechanical level, proposing illustrative examples of model situations of nonadiabatic dynamics and spontaneous emission of electron–nuclear systems in the regime of strong light–matter coupling. We make a particular choice of factorization for such a multi-component system, where the full wavefunction is factored as a conditional electronic amplitude and a marginal photon–nuclear amplitude. Then, we apply the coupled-trajectory mixed quantum–classical (CTMQC) algorithm to perform trajectory-based simulations, by treating photonic and nuclear degrees of freedom on equal footing in terms of classical-like trajectories. The analysis of the time-dependent potentials of the theory along with the assessment of the performance of CTMQC allows us to point out some limitations of the current approximations used in CTMQC. Meanwhile, comparing CTMQC with other trajectory-based algorithms, namely multi-trajectory Ehrenfest and Tully surface hopping, demonstrates the better quality of CTMQC predictions. [ABSTRACT FROM AUTHOR]

Details

Language :
English
ISSN :
00219606
Volume :
161
Issue :
8
Database :
Academic Search Index
Journal :
Journal of Chemical Physics
Publication Type :
Academic Journal
Accession number :
179372620
Full Text :
https://doi.org/10.1063/5.0224779