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Towards the Realization of Ab Initio Dynamics at the Speed of Molecular Mechanics: Simulations with Interpolated Diabatic Hamiltonian
Author(s) -
Park Jae Woo,
Rhee Young Min
Publication year - 2014
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201402226
Subject(s) - diabatic , adiabatic process , ab initio , hamiltonian (control theory) , vibronic coupling , molecular dynamics , potential energy , statistical physics , chromophore , chemistry , ab initio quantum chemistry methods , realization (probability) , speedup , computational chemistry , reaction dynamics , physics , quantum mechanics , computer science , excited state , molecule , mathematics , mathematical optimization , statistics , operating system
Understanding photochemical processes often requires accurate descriptions of the nonadiabatic events involved. The cost of accurate quantum chemical simulations of the nonadiabatic dynamics of complex systems is typically high. Here, we discuss the use of interpolated quasi‐diabatic potential‐energy matrices, which aims to reduce the computational cost with minimal sacrifices in accuracy. It is shown that interpolation reproduces the reference ab initio information satisfactorily for a sizeable chromophore in terms of its adiabatic energies and derivative coupling vectors. Actual nonadiabatic simulation results of the chromophore in the gas phase and in aqueous solution are presented, and it is demonstrated that the interpolated quasi‐diabatic Hamiltonian can be applied to studying nonadiabatic events of a complex system in an ensemble manner at a much‐reduced cost. Limitations, and how they can be overcome in future studies, are also discussed.