Theory Department
Max Planck Institute of Microstructure Physics
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Min, S.-K., Agostini, F., Tavernelli, I., Gross, E. K. U.

Ab-initio nonadiabatic dynamics with coupled trajectories: A rigorous approach to quantum (de)coherence
Journal of Physical Chemistry Letters 8, (13),pp 3048-3055 (2017)
We report the first nonadiabatic molecular dynamics study based on the exact factorization of the electron-nuclear wave function. Our approach (a coupled-trajectory mixed quantum-classical, CT-MQC, scheme) is based on the quantum-classical limit derived from systematic and controlled approximations to the full quantum-mechanical problem formulated in the exact-factorization framework. Its strength is the ability to correctly capture quantum (de)coherence effects in a trajectory-based approach to excited-state dynamics. We show this by benchmarking CT-MQC dynamics against a revised version of the popular fewest-switches surface-hopping scheme that is able to fix its well-documented overcoherence issue. The CT-MQC approach is successfully applied to investigation of the photochemistry (ring-opening) of oxirane in the gas phase, analyzing in detail the role of decoherence. This work represents a significant step forward in the establishment of the exact factorization as a powerful tool to study excited-state dynamics, not only for interpretation purposes but mainly for nonadiabatic ab initio molecular dynamics simulations.

TH-2017-23