Nonadiabatic kinetics in the intermediate coupling regime: comparing molecular dynamics to an energy grained master equation

Darya Shchepanovska, Robin J Shannon, Basile Curchod*, David R Glowacki*

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

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 nonadiabatic passages beyond the simple Landau-Zener approximation, along with corresponding treatments of zero-point energy and tunnelling probability. To evaluate the performance of this NA-EGME approach, we carried out detailed studies of the UV photodynamics of the volatile organic compound C6-hydroperoxyaldehyde (C6-HPALD) using on-the-fly ab initio molecular dynamics and trajectory surface hopping. For this multi-chromophore 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.
Original languageEnglish
JournalJournal of Physical Chemistry A
Early online date21 Apr 2021
Publication statusE-pub ahead of print - 21 Apr 2021

Fingerprint

Dive into the research topics of 'Nonadiabatic kinetics in the intermediate coupling regime: comparing molecular dynamics to an energy grained master equation'. Together they form a unique fingerprint.

Cite this