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Nature of hops, coordinates, and detailed balance for nonadiabatic simulations in the condensed phase

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. Nonadia...

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Main Authors: Menger, Maximilian (Author) , Ou, Qi (Author) , Shao, Yihan (Author) , Faraji, Shirin (Author) , Subotnik, Joseph E. (Author) , Cofer-Shabica, D. Vale (Author)
Format: Article (Journal)
Language:English
Published: October 12, 2023
In: The journal of physical chemistry. A, Molecules, clusters, and aerosols
Year: 2023, Volume: 127, Issue: 40, Pages: 8427-8436
ISSN:1520-5215
DOI:10.1021/acs.jpca.3c03546
Online Access:Verlag, lizenzpflichtig, Volltext: https://doi.org/10.1021/acs.jpca.3c03546
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Author Notes:Maximilian F.S.J. Menger, Qi Ou, Yihan Shao, Shirin Faraji, Joseph E. Subotnik, D. Vale Cofer-Shabica
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Summary: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.
Item Description:Online veröffentlicht: 02. Oktober 2023
Gesehen am 04.12.2023
Physical Description:Online Resource
ISSN:1520-5215
DOI:10.1021/acs.jpca.3c03546

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