Approximate quantum trajectory dynamics for reactive processes in condensed phase

作者：Garashchuk Sophya^*; Jakowski Jacek; Rassolov Vitaly A

来源：Molecular Simulation, 2015, 41(1-3): 86-106.

DOI：10.1080/08927022.2014.907493

• density-functional tight-binding method
• hybrid dynamics of quantum/classical nuclei
• quantum effect
• on-the-fly electronic structure

A method of molecular dynamics with quantum corrections, practical for studies of large molecular systems, is reviewed. The approach is based on the Bohmian formulation of the time-dependent Schrodinger equation in which a wavefunction is represented by an ensemble of interdependent trajectories. The quantum effects come from the quantum potential acting on trajectories on par with the usual classical potential. The quantum potential is determined from the evolving nuclear wavefunction, i.e. from the quantum trajectory (QT) ensemble itself. For practical and conceptual reasons the quantum potential and corresponding quantum nuclear effect are computed only for the selected light nuclei. For studies of reactive chemical processes, the classical potential is computed on-the-fly using the density functional tight binding method of electronic structure. A massively parallel implementation, based on the message passing interface allows for efficient simulations of ensembles of thousands of trajectories describing systems of up to 200 atoms. As a biochemical application, the approximate QT approach is used to model the tunnelling-dominated proton transfer in soybean-lipoxygenase-1. A materials science application is represented by a study of the nuclear quantum effect on adsorption of hydrogen and deuterium on a C37H15 molecule, which is a model 'flake' of graphene.

• 出版日期2015-2-11