Best practices for nonadiabatic molecular dynamics simulations [Article v1.0]

Abstract

Nonadiabatic molecular dynamics simulations aim to describe the coupled electron- nuclear dynamics of molecules in excited electronic states, beyond the celebrated Born-Oppenheimer approximation. These simulations have been applied to understand a plethora of photochemical and photophysical processes and to support the interpretation of ultrafast spectroscopy experiments at advanced light sources. As a result, the number of nonadiabatic dynamics simulations has been growing significantly over the past decade. Yet, the field remains in its infancy, and a potential user may find it difficult to approach this type of simulation, given their complexity and the number of elements that should be considered for a (hopefully) successful nonadiabatic dynamics simulation. Nonadiabatic molecular dynamics relies on several key steps: finding a level of electronic-structure theory to describe the molecule in its Franck-Condon region and beyond, describing the photoexcitation process, selecting a method to perform the nonadiabatic dynamics, and analyzing the final results before calculating observables for a more direct comparison with experiment. This Best Practices guide aims to provide a general guide for the user of nonadiabatic molecular dynamics by (i) discussing the fundamentals of nonadiabatic molecular dynamics and the various trajectory-based methods developed for molecular systems, (ii) introducing the different electronic-structure methods and concepts – adiabatic/diabatic representation, conical intersections – that can be used with nonadiabatic molecular dynamics (or for benchmarking), (iii) providing details on the various steps required to perform a nonadiabatic dynamics simulation and their practical use, as well as guided examples and a discussion on the calculation of observables, (iv) proposing a FAQ with the typical questions a user may have when performing nonadiabatic dynamics, and (v) sketching a checklist for the key practical steps when performing a (trajectory-based) nonadiabatic molecular dynamics. Each section is self-contained, but we endeavor to provide additional key references for each concept discussed, making this Guide a starting point for the interested reader to dig further into the field of nonadiabatic dynamics.