An exact factorization perspective on quantum interferences in nonadiabatic dynamics

Curchod, Basile F.E.; Agostini, Federica; Gross, E.K.U.

Abstract

Nonadiabatic quantum interferences emerge whenever nuclear wavefunctions in different electronic states meet and interact in a nonadiabatic region. In this work, we analyze how nonadiabatic quantum interferences translate in the context of the exact factorization of the molecular wavefunction. In particular, we focus our attention on the shape of the time-dependent potential energy surface—the exact surface on which the nuclear dynamics takes place. We use a one-dimensional exactly solvable model to reproduce different conditions for quantum interferences, whose characteristic features already appear in one-dimension. The time-dependent potential energy surface develops complex features when strong interferences are present, in clear contrast to the observed behavior in simple nonadiabatic crossing cases. Nevertheless, independent classical trajectories propagated on the exact time-dependent potential energy surface reasonably conserve a distribution in configuration space that mimics one of the exact nuclear probability densities.

Citation

Curchod, B. F., Agostini, F., & Gross, E. (2016). An exact factorization perspective on quantum interferences in nonadiabatic dynamics. The Journal of Chemical Physics, 145(3), Article 034103. https://doi.org/10.1063/1.4958637

• Journal Article Type: Article
• Acceptance Date: Jun 29, 2016
• Online Publication Date: Jul 18, 2016
• Publication Date: Jul 18, 2016
• Deposit Date: Nov 6, 2017
• Publicly Available Date: Dec 8, 2017
• Journal: Journal of Chemical Physics
• Print ISSN: 0021-9606
• Electronic ISSN: 1089-7690
• Publisher: American Institute of Physics
• Peer Reviewed: Peer Reviewed
• Volume: 145
• Issue: 3
• Article Number: 034103
• DOI: https://doi.org/10.1063/1.4958637
• Public URL: https://durham-repository.worktribe.com/output/1344670