| Title: | Nonadiabatic Kinetics in the Intermediate Coupling Regime: Comparing Molecular Dynamics to an Energy-Grained Master Equation |
| Author(s): | Shchepanovska D; Shannon RJ; Curchod BFE; Glowacki DR; |
| Address: | "School of Chemistry, University of Bristol, Bristol BS8 1TS, U.K. Department of Chemistry, Durham University, Durham DH1 3LE, U.K. Intangible Realities Laboratory, University of Bristol, Bristol BS8 1UB, U.K. Department of Computer Science, University of Bristol, Bristol BS8 1UB, U.K" |
| ISSN/ISBN: | 1520-5215 (Electronic) 1089-5639 (Linking) |
| Abstract: | "We propose and test an extension of the energy-grained master equation (EGME) for treating nonadiabatic (NA) hopping between different potential energy surfaces, which enables us to model the competition between stepwise collisional relaxation and kinetic processes which transfer population between different electronic states of the same spin symmetry. By incorporating Zhu-Nakamura theory into the EGME, we are able to treat NA passages beyond the simple Landau-Zener approximation, along with the corresponding treatments of zero-point energy and tunneling probability. To evaluate the performance of this NA-EGME approach, we carried out detailed studies of the UV photodynamics of the volatile organic compound C(6)-hydroperoxy aldehyde (C(6)-HPALD) using on-the-fly ab initio molecular dynamics and trajectory surface hopping. For this multichromophore molecule, we show that the EGME is able to capture important aspects of the dynamics, including kinetic timescales, and diabatic trapping. Such an approach provides a promising and efficient strategy for treating the long-time dynamics of photoexcited molecules in regimes which are difficult to capture using atomistic on-the-fly molecular dynamics" |
| Notes: | "PubMed-not-MEDLINEShchepanovska, Darya Shannon, Robin J Curchod, Basile F E Glowacki, David R eng 2021/04/22 J Phys Chem A. 2021 Apr 29; 125(16):3473-3488. doi: 10.1021/acs.jpca.1c01260. Epub 2021 Apr 21" |
