Ab Initio Nonadiabatic Dynamics with Coupled Trajectories: A Rigorous Approach to Quantum (De)Coherence

Seung Kyu Min*, Federica Agostini, Ivano Tavernelli, E. K.U. Gross

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

123 Scopus citations

Abstract

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.

Original languageAmerican English
Pages (from-to)3048-3055
Number of pages8
JournalJournal of Physical Chemistry Letters
Volume8
Issue number13
DOIs
StatePublished - 6 Jul 2017
Externally publishedYes

Bibliographical note

Publisher Copyright:
© 2017 American Chemical Society.

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