Geometric phase effects in excited state dynamics through a conical intersection in large molecules: N-dimensional linear vibronic coupling model study

TL;DR

This study explores how geometric phase effects influence nonadiabatic transitions in large molecules using an N-dimensional vibronic coupling model, highlighting parameter conditions that affect symmetry and GP effects.

Contribution

It introduces a 2D subsystem approach within an N-dimensional model to analyze geometric phase effects in conical intersection dynamics.

Findings

Parameters can break symmetry and reduce GP effects.

The 2D subsystem effectively captures ultrafast nonadiabatic dynamics.

Model links ND-LVC parameters to GP influence.

Abstract

We investigate geometric phase (GP) effects in nonadiabatic transitions through a conical intersection (CI) in an N-dimensional linear vibronic coupling (ND-LVC) model. This model allows for the coordinate transformation encompassing all nonadiabatic effects within a two-dimensional (2D) subsystem while the other N-2 dimensions form a system of uncoupled harmonic oscillators identical for both electronic states and coupled bi-linearly with the subsystem coordinates. The 2D subsystem governs ultra-fast nonadiabatic dynamics through the CI and provides a convenient model for studying GP effects. Parameters of the original ND-LVC model define the Hamiltonian of the transformed 2D subsystem and thus influence GP effects directly. Our analysis reveals what values of ND-LVC parameters can introduce symmetry breaking in the 2D subsystem that diminishes GP effects.