State-To-State Inelastic Rotational Cross Sections in Five-Atom Systems with the Multiconfiguration Time Dependent Hartree Method
We present a MultiConfiguration Time Dependent Hartree (MCTDH) method as an attractive alternative approach to the usual quantum close-coupling method that approaches some computational limits in the calculation of rotational excitation (and de-excitation) between polyatomic molecules (here collisions between triatomic and diatomic rigid molecules). We have performed a computational investigation of the rotational (de-)excitation of the benchmark rigid rotor H2O-H2 system on a recently developed Potential Energy Surface of the complex using the MCTDH method. We focus here on excitations and de-excitations from the 000, 111, and 110 states of H2O with H2 in its ground rotational state, looking at all the potential transitions in the energy range 1-200 cm-1. This work follows a recently completed study on the H2O-H2 cluster where we characterized its spectroscopy and more generally serves a broader goal to describe inelastic collision processes of high dimensional systems using the MCTDH method. We find that the cross sections obtained from the MCTDH calculations are in excellent agreement with time independent calculations from previous studies but does become challenging for the lower kinetic energy range of the de-excitation process: that is, below approximately 20 cm-1 of collision energy, calculations with a relative modest basis become unreliable. The MCTDH method therefore appears to be a useful complement to standard approaches to study inelastic collision for various collision partners, even at low energy, though performing better for rotational excitation than for de-excitation.
S. Ndengue et al., "State-To-State Inelastic Rotational Cross Sections in Five-Atom Systems with the Multiconfiguration Time Dependent Hartree Method," Journal of Chemical Physics, vol. 151, no. 13, American Institute of Physics (AIP), Oct 2019.
The definitive version is available at https://doi.org/10.1063/1.5119381
Center for High Performance Computing Research
Keywords and Phrases
Kinetic energy; Kinetics; Molecules; Plasma collision processes; Potential energy; Quantum chemistry, Close-coupling method; Computational investigation; Ground rotational state; High-dimensional systems; Inelastic collision; Multiconfiguration time-dependent hartree method; Polyatomic molecules; Rotational excitation, Polymer films
International Standard Serial Number (ISSN)
Article - Journal
© 2019 The Authors, All rights reserved.
01 Oct 2019
This research was supported by the U.S. Department of Energy Office of Science, Office of Basic Energy Sciences (Award No. DESC0019740) to R.D.