Oscillatory reaction cross sections caused by normal mode sampling in quasiclassical trajectory calculations

Tibor Nagy, Anna Vikár, G. Lendvay

Research output: Contribution to journalArticle

5 Citations (Scopus)

Abstract

The quasiclassical trajectory (QCT) method is an efficient and important tool for studying the dynamics of bimolecular reactions. In this method, the motion of the atoms is simulated classically, and the only quantum effect considered is that the initial vibrational states of reactant molecules are semiclassically quantized. A sensible expectation is that the initial ensemble of classical molecular states generated this way should be stationary, similarly to the quantum state it is supposed to represent. The most widely used method for sampling the vibrational phase space of polyatomic molecules is based on the normal mode approximation. In the present work, it is demonstrated that normal mode sampling provides a nonstationary ensemble even for a simple molecule like methane, because real potential energy surfaces are anharmonic in the reactant domain. The consequences were investigated for reaction CH4 + H → CH3 + H2 and its various isotopologs and were found to be dramatic. Reaction probabilities and cross sections obtained from QCT calculations oscillate periodically as a function of the initial distance of the colliding partners and the excitation functions are erratic. The reason is that in the nonstationary ensemble of initial states, the mean bond length of the breaking C-H bond oscillates in time with the frequency of the symmetric stretch mode. We propose a simple method, one-period averaging, in which reactivity parameters are calculated by averaging over an entire period of the mean C-H bond length oscillation, which removes the observed artifacts and provides the physically most reasonable reaction probabilities and cross sections when the initial conditions for QCT calculations are generated by normal mode sampling.

Original languageEnglish
Article number014104
JournalThe Journal of Chemical Physics
Volume144
Issue number1
DOIs
Publication statusPublished - Jan 7 2016

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sampling
Trajectories
trajectories
Bond length
Sampling
Molecules
cross sections
Potential energy surfaces
Methane
polyatomic molecules
vibrational states
artifacts
molecules
Atoms
methane
reactivity
potential energy
oscillations
approximation
excitation

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

Cite this

Oscillatory reaction cross sections caused by normal mode sampling in quasiclassical trajectory calculations. / Nagy, Tibor; Vikár, Anna; Lendvay, G.

In: The Journal of Chemical Physics, Vol. 144, No. 1, 014104, 07.01.2016.

Research output: Contribution to journalArticle

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