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