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

109 Scopus citations


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
Issue number13
StatePublished - 6 Jul 2017
Externally publishedYes

Bibliographical note

Funding Information:
S.K.M. acknowledges financial support from the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (2016R1C1B2015103) and the 2015 Research Fund (1.150115.01) of UNIST (Ulsan National Institute of Science & Technology). I.T. acknowledges the Swiss National Centres of Competence in Research (NCCR) MARVEL for its support.

Publisher Copyright:
© 2017 American Chemical Society.


Dive into the research topics of 'Ab Initio Nonadiabatic Dynamics with Coupled Trajectories: A Rigorous Approach to Quantum (De)Coherence'. Together they form a unique fingerprint.

Cite this