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Issue 19, 2018
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A general formulation of the quasiclassical trajectory method for reduced-dimensionality reaction dynamics calculations

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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

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Publication details

The article was received on 12 Mar 2018, accepted on 17 Apr 2018 and first published on 18 Apr 2018


Article type: Paper
DOI: 10.1039/C8CP01600C
Citation: Phys. Chem. Chem. Phys., 2018,20, 13224-13240
  • Open access: Creative Commons BY-NC license
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    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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