An exact factorization perspective on quantum interferences in nonadiabatic dynamics

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 pa...

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Bibliographic Details
Published in:The Journal of chemical physics 2016-07, Vol.145 (3), p.034103-034103
Main Authors: Curchod, Basile F. E., Agostini, Federica, Gross, E. K. U.
Format: Article
Language:English
Subjects:
ELECTRIC POTENTIAL
Electron states
Energy conservation
EXACT SOLUTIONS
FACTORIZATION
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
INTERFERENCE
POTENTIAL ENERGY
SURFACES
TIME DEPENDENCE
WAVE FUNCTIONS
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Summary: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.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4958637