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

Nagy, Tibor and Vikár, Anna and Lendvay, György (2018) A general formulation of the quasiclassical trajectory method for reduced-dimensionality reaction dynamics calculations. Physical Chemistry Chemical Physics, 20 (19). pp. 13224-13240. ISSN 1463-9076

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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 [Vikár et al., J. Phys. Chem. A 120 (2016) 5083–5093.]

Item Type: Article
Subjects: Q Science / természettudomány > QC Physics / fizika > QC01 Mechanics / mechanika
Q Science / természettudomány > QD Chemistry / kémia > QD02 Physical chemistry / fizikai kémia
Depositing User: Tibor Nagy
Date Deposited: 01 Oct 2018 12:48
Last Modified: 02 Oct 2018 06:50

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