Issue 19, 2018

A general formulation of the quasiclassical trajectory method for reduced-dimensionality reaction dynamics calculations

Abstract

Dimension reduction by freezing the unimportant coordinates is widely used in intramolecular and reaction dynamics calculations when the solution of the accurate full-dimensional nuclear Schrödinger equation is not feasible. In this paper we report on a novel form of the exact classical internal-coordinate Hamiltonian for full and reduced-dimensional vibrational motion of polyatomic molecules with the purpose of using it in quasiclassical trajectory (QCT) calculations. The derivation is based on the internal to body-fixed frame transformation, as in the t-vector formalism, however it does not require the introduction of rotational variables to allow cancellation of non-physical rotations within the body-fixed frame. The formulas needed for QCT calculations: normal mode analysis and state sampling as well as for following the dynamics and normal-mode quantum number assignment at instantaneous states are presented. The procedure is demonstrated on the CH4, CD4, CH3D and CHD3 isotopologs of methane using three reduced-dimensional models, which were previously used in quantum reactive scattering studies of the CH4 + X → CH3 + HX type reactions. The reduced-dimensional QCT methodology formulated this way combined with full-dimensional QCT calculations makes possible the classical validation of reduced-dimensional models that are used in the quantum mechanical description of the nuclear dynamics in reactive systems [A. Vikár et al., J. Phys. Chem. A, 2016, 120, 5083–5093].

Graphical abstract: A general formulation of the quasiclassical trajectory method for reduced-dimensionality reaction dynamics calculations

Supplementary files

Article information

Article type
Paper
Submitted
12 Mar 2018
Accepted
17 Apr 2018
First published
18 Apr 2018
This article is Open Access
Creative Commons BY-NC license

Phys. Chem. Chem. Phys., 2018,20, 13224-13240

A general formulation of the quasiclassical trajectory method for reduced-dimensionality reaction dynamics calculations

T. Nagy, A. Vikár and G. Lendvay, Phys. Chem. Chem. Phys., 2018, 20, 13224 DOI: 10.1039/C8CP01600C

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