Efficient fourth-order split operator for solving the triatomic reactive Schrödinger equation in the time-dependent wavepacket approach.

Abstract

An efficient fourth-order split operator (named 4A6a in the main text), which was presented in the work by Blanes and Moan and was a partitioned Runge-Kutta method ( J. Comput. Appl. Math. 2002 , 142 , 313 ), is recommended for general usage in a reactive scattering calculation by the time-dependent quantum wavepacket method. This 4A6a propagator is constructed in a TVT form, that is, splitting in kinetic-potential-kinetic form, which is an optimal one among a series of higher-order split operators in examining with several typical triatomic reactive scattering processes, H + H2, H + H2(+), H + NH, H + O2, and F + HD reactions. A detailed comparison between the performances of higher-order split operators in the VTV form, that is, splitting in a potential-kinetic-potential, which was reported by Sun et al. ( Phys. Chem. Chem. Phys. 2012 , 14 , 1827 ), and in the TVT form reported in the current work suggests that the recommended 4A6a operator in the TVT form always has good numerical efficiency. This fact may suggest that this fourth propagator in the TVT form can be safely chosen without any further examination, at least among all of the higher-order split operators tested in this work, to apply in an efficient time-dependent wavepacket numerical calculation for describing a triatomic reactive scattering process.