Which Electronic Structure Method to Choose in Trajectory Surface Hopping Dynamics Simulations? Azomethane as a Case Study

TL;DR

This study evaluates various electronic structure methods for non-adiabatic dynamics simulations, highlighting the superiority of multi-reference methods and the limitations of TD-DFT and ADC(2) in accurately modeling photochemical decay pathways.

Contribution

It provides a benchmark comparison of multiple electronic structure methods against high-accuracy XMS-CASPT2 for trajectory surface hopping simulations.

Findings

Multi-reference methods are preferred for non-adiabatic decay studies.

TD-DFT with TDA and hybrid functionals overestimate decay yields.

ADC(2) offers an efficient alternative but may miss pathways.

Abstract

Non-adiabatic dynamics simulations have become a standard approach to explore photochemical reactions. Such simulations require underlying potential energy surfaces and couplings between them, calculated at a chosen level of theory, yet this aspect is rarely assessed. Here, in combination with the popular trajectory surface hopping dynamics method, we use a high-accuracy XMS-CASPT2 electronic structure level as a benchmark for assessing the performances of various post-Hartree-Fock methods (namely CIS, ADC(2), CC2 and CASSCF) and exchange-correlation functionals (PBE, PBE0, CAM-B3LYP) in a TD-DFT/TDA context, using the isomerization around a double bond as test case. Different relaxation pathways are identified, and the ability of the different methods to reproduce their relative importance and timescale is discussed. The results show that multi-reference electronic structure methods should be preferred, when studying non-adiabatic decay between excited and ground states. If not affordable, TD-DFT with TDA and hybrid functionals, and ADC(2) are efficient alternative, but overestimate the non-radiative decay yield and thus may miss deexcitation pathways.