# Molecular Origin of Correlated Bath Effects in Photoinduced Charge Transfer Dynamics in Polar Solvents

## TL;DR

This paper explores how environmental correlations in polar solvents influence charge transfer dynamics after light absorption.

## Contribution

A geometric metric is proposed to quantify bath correlations in multistate nonadiabatic dynamics.

## Key findings

- Correlated baths synchronize energy fluctuations to facilitate competing reactions.
- Anticorrelated baths suppress one reaction when favoring another.
- Molecular conformation and dipole moments modulate energetic correlations.

## Abstract

Nonadiabatic dynamics
in the condensed phase often involve correlated
environments shared by multiple electronic states, challenging the
traditional isolated bath assumption. We investigate these effects
using the multistate harmonic (MSH) model and atomistic Hamiltonian
applied to photoinduced charge transfer in a trimer consisting of
a methylperylene donor and two tetracyanoethylene acceptors dissolved
in a polar solvent. We propose a geometric metric based on the angular
relationship of reorganization energies between transitions sharing
an initial state to quantify bath correlation. Our analysis identifies
distinct regimes: a correlated bath where synchronized energy gap
fluctuations facilitate competing reactions, and an anticorrelated
bath where fluctuations favoring one reaction suppress the other.
These energetic correlations are modulated by molecular conformation
and charge distribution, specifically through changes in dipole moments
and solvent-accessible surface area. This study provides a connection
between the energetic perspective of environmental correlations and
the molecular details governing nonadiabatic dynamics in polar solvents.