Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

Rachel Crespo-Otero (1) , Mario Barbatti (2)

1 QMUL - Queen Mary University of London
2 ICR - Institut de Chimie Radicalaire

Nonadiabatic mixed quantum-classical (NA-MQC) dynamics methods form a class of computational theoretical approaches in quantum chemistry, tailored to investigate the time-evolution of nonadiabatic phenomena in molecules and supramolecular assemblies. NA-MQC ischaracterized by a partitionof the molecular system into two subsystems, one to be treated quantum-mechanically (usually, but not restricted to electrons); and another to be dealt with classically (nuclei). The two subsystems are connected through nonadiabatic couplings terms, to enforce self-consistency. A local approximation underlies the classical subsystem, implying that direct dynamics can be simulated, without needing pre-computed potential energy surfaces. The NA-MQC split allows reducing computational costs, enabling the treatment of realistic molecular systems in diverse fields. Starting from the three most well-established methods—mean-field Ehrenfest, trajectory surface hopping, and multiple spawning, this review focus on the NA-MQC dynamics methods and programs developed in the last ten years. It stresses the relations between approaches and their domains of application. The electronic structure methods most commonly used together with NA-MQC dynamics are reviewed as well. The accuracy and precision of NA-MQC simulations are critically discussed, and general guidelinesto choosean adequate method for each application are delivered.

Keywords: Nonadiabatic; Quantum classical (NA-MQC); Quantum mechanically; Ehrenfest classification; NA-MQC

Domains: Chemical Sciences; Chemical Sciences; Theoretical and/or physical chemistry

Rachel Crespo-Otero, Mario Barbatti. Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics. Chemical Reviews, 2018, 118 (15), pp.7026-7068. ⟨10.1021/acs.chemrev.7b00577⟩. ⟨hal-01965458⟩