Nonadiabatic simulations of photoisomerization and dissociation in ethylene using ab initio classical trajectories

TL;DR

This study employs a semiclassical ab initio trajectory method to simulate nonadiabatic photoisomerization and dissociation in ethylene, revealing mechanistic pathways consistent with prior theories and experimental observations.

Contribution

It introduces a parameter-free semiclassical approach using LSC-IVR with spin mapping for efficient nonadiabatic dynamics simulations.

Findings

Identifies mechanistic pathways consistent with previous studies.

Uncovers dissociation pathways observed experimentally.

Demonstrates computational efficiency and accuracy of the method.

Abstract

We simulate the nonadiabatic dynamics of photo-induced isomerization and dissociation in ethylene using ab initio classical trajectories in an extended phase space of nuclear and electronic variables. This is achieved by employing the Linearized Semiclassical Initial Value Representation (LSC-IVR) method for nonadiabatic dynamics where discrete electronic states are mapped to continuous classical variables using either the Meyer-Miller Stock-Thoss representation or a more recently introduced spin mapping approach. Trajectory initial conditions are sampled by constraining electronic state variables to a single initial excited state, and by drawing nuclear phase space configurations from a Wigner distribution at finite temperature. An ensemble of classical ab initio trajectories are then generated to compute thermal population correlation functions and to analyze the mechanisms of isomerization and dissociation. Our results serve as a demonstration that this parameter-free semiclassical approach is computationally efficient and accurate, identifying mechanistic pathways in agreement with previous theoretical studies, and also uncovering dissociation pathways observed experimentally.