An Exact Factorization Perspective on Quantum Interferences in Nonadiabatic Dynamics

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 the one of the exact nuclear probability density.

Accepted in J. Chem. Phys

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Cited by in corpus (6)

• Ultrafast dynamics with the exact factorization
• On the Numerical Solution of the Exact Factorization Equations
• Bohmian mechanics in the exact factorization of electron-nuclear wavefunction
• Case Studies of the Time-Dependent Potential Energy Surface for Dynamics in Cavities
• Quantum-classical nonadiabatic dynamics of Floquet driven systems
• Conditional wave theory of environmental interactions with a quantum particle