Simulations of molecular photodynamics in long timescales

Saikat Mukherjee (1) , Max Pinheiro (1) , Baptiste Demoulin (1) , Mario Barbatti (1, 2)

1 ICR - Institut de Chimie Radicalaire
2 IUF - Institut universitaire de France

Nonadiabatic dynamics simulations in the long timescale (much longer than 10 ps) are the next challenge in computational photochemistry. This paper delimits the scope of what we expect from methods to run such simulations: they should work in full nuclear dimensionality, be general enough to tackle any type of molecule, and not require unrealistic computational resources. We examine the main methodological challenges we should venture to advance the field, including the computational costs of the electronic structure calculations, stability of the integration methods, accuracy of the nonadiabatic dynamics algorithms, and software optimization. Based on simulations designed to shed light on each of these issues, we show how machine learning may be a crucial element for long-timescale dynamics, either as a surrogate for electronic structure calculations or aiding the parameterization of model Hamiltonians. We show that conventional methods for integrating classical equations should be adequate to extended simulations up to 1 ns and that surface hopping agrees semi-quantitatively with wavepacket propagation in the weak-coupling regime. We also describe our optimization of the Newton-X program to reduce computational overheads in data processing and storage.

Mots clés: computational chemistry; photochemistry; physical chemistry theoretical chemistry; excited states; nonadiabatic phenomena; dynamics simulations

Domaines: Chimie; Chimie théorique et/ou physique

Saikat Mukherjee, Max Pinheiro, Baptiste Demoulin, Mario Barbatti. Simulations of molecular photodynamics in long timescales. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, 2022, 380 (2223), ⟨10.1098/rsta.2020.0382⟩. ⟨hal-03625294⟩