TY - JOUR
T1 - Nature of Hops, Coordinates, and Detailed Balance for Nonadiabatic Simulations in the Condensed Phase
AU - Menger, Maximilian F.S.J.
AU - Ou, Qi
AU - Shao, Yihan
AU - Faraji, Shirin
AU - Subotnik, Joseph E.
AU - Cofer-Shabica, D. Vale
N1 - Publisher Copyright:
© 2023 American Chemical Society.
PY - 2023/10/12
Y1 - 2023/10/12
N2 - 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.
AB - 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.
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U2 - 10.1021/acs.jpca.3c03546
DO - 10.1021/acs.jpca.3c03546
M3 - Article
C2 - 37782887
AN - SCOPUS:85175585801
SN - 1089-5639
VL - 127
SP - 8427
EP - 8436
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 40
ER -