Including photoexcitation explicitly in trajectory-based nonadiabatic dynamics at no cost

TL;DR

This paper introduces a novel formalism called promoted density approach (PDA) that explicitly incorporates laser photoexcitation effects into trajectory-based nonadiabatic molecular dynamics without additional computational cost, improving simulation accuracy.

Contribution

The authors develop PDA to include laser pulse effects directly in initial conditions for nonadiabatic dynamics, enabling more realistic simulations at no extra cost.

Findings

PDA accurately reproduces quantum dynamics with explicit laser pulses.

Laser pulses significantly influence photodynamics and the validity of vertical excitation assumptions.

The method is applicable to molecules of arbitrary size using provided code.

Abstract

Over the last decades, theoretical photochemistry has produced multiple techniques to simulate the nonadiabatic dynamics of molecules. Surprisingly, much less effort has been devoted to adequately describing the first step of a photochemical or photophysical process: photoexcitation. Here, we propose a formalism to include the effect of a laser pulse in trajectory-based nonadiabatic dynamics at the level of the initial conditions, with no additional cost. The promoted density approach (PDA) decouples the excitation from the nonadiabatic dynamics by defining a new set of initial conditions, which include an excitation time. PDA with surface hopping leads to nonadiabatic dynamics simulations in excellent agreement with quantum dynamics using an explicit laser pulse and highlights the strong impact of a laser pulse on the resulting photodynamics and the limits of the (sudden) vertical excitation. Combining PDA with trajectory-based nonadiabatic methods is possible for any arbitrary-sized molecules using a code provided in this work.