CT-MQC – A Coupled-Trajectory Mixed Quantum/Classical method including nonadiabatic quantum coherence effects

Abstract

Upon photoexcitation by a short light pulse, molecules can reach regions of the configuration space characterized by strong nonadiabaticity, where the motion of the nuclei is strongly coupled to the motion of the electrons. The subtle interplay between the nuclear and electronic degrees of freedom in such situations is rather challenging to capture by state-of-the-art nonadiabatic dynamics approaches, limiting therefore their predictive power. The Exact Factorization of the molecular wavefunction, though, offers new perspectives in the solution of this longstanding issue. Here, we investigate the performance of a mixed quantum/classical (MQC) limit of this theory, named Coupled Trajectory-MQC, which was shown to reproduce the excited-state dynamics of small systems accurately. The method is applied to the study of the photoinduced ring opening of oxirane and the results are compared with two other nonadiabatic approaches based on different Ansätze for the molecular wavefunction, namely Ehrenfest dynamics and Ab Initio Multiple Spawning (AIMS). All simulations were performed using linear-response time-dependent density functional theory. We show that the CT-MQC method can capture the (de)coherence effects resulting from the dynamics through conical intersections, in good agreement with the results obtained with AIMS and in contrast with ensemble Ehrenfest dynamics.