Nature of Hops, Coordinates, and Detailed Balance for Nonadiabatic Simulations in the Condensed Phase

Maximilian F.S.J. Menger, Qi Ou, Yihan Shao, Shirin Faraji, Joseph E. Subotnik, D. Vale Cofer-Shabica

Research output: Contribution to journalArticlepeer-review

4 Scopus citations

Abstract

Photoinduced processes play a crucial role in a multitude of important molecular phenomena. Accurately modeling these processes in an environment other than a vacuum requires a detailed description of the electronic states involved as well as how energy flows are coupled to the surroundings. Nonadiabatic effects must also be included in order to describe the exchange of energy between electronic and nuclear degrees of freedom correctly. In this work, we revisit the ring-opening reaction 1,3-cylohexadiene (CHD) in a solvent environment. Using our newly developed Interface for Non-Adiabatic Quantum mechanics/molecular mechanics in Solvent (INAQS) we trace the evolution of the reaction via hybrid quantum mechanics/molecular mechanics (QM/MM) surface hopping with a focus on the solvent’s participation in the nonadiabatic relaxation process and the long-time approach to equilibrium. We explicitly include the MM solvent contribution to the nonadiabatic coupling vector─enabling an accurate approach to equilibrium at long times─and find that in highly multidimensional systems gradients can have little or nothing to do with the nonadiabatic couplings.

Original languageEnglish (US)
Pages (from-to)8427-8436
Number of pages10
JournalJournal of Physical Chemistry A
Volume127
Issue number40
DOIs
StatePublished - Oct 12 2023
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

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