Quantum mechanical reaction rate constants by vibrational configuration interaction: The OH + H2→H2O + H reaction as a function of temperature

Arindam Chakraborty, Donald G. Truhlar

Research output: Contribution to journalArticle

17 Scopus citations

Abstract

The thermal rate constant of the 3D OH + H2→H2O + H reaction was computed by using the flux autocorrelation function, with a time-independent square-integrable basis set. Two modes that actively participate in bond making and bond breaking were treated by using 2D distributed Gaussian functions, and the remaining (nonreactive) modes were treated by using harmonic oscillator functions. The finite-basis eigenvalues and eigenvectors of the Hamiltonian were obtained by solving the resulting generalized eigenvalue equation, and the flux autocorrelation function for a dividing surface optimized in reduced-dimensionality calculations was represented in the basis formed by the eigenvectors of the Hamiltonian. The rate constant was obtained by integrating the flux autocorrelation function. The choice of the final time to which the integration is carried was determined by a plateau criterion. The potential energy surface was from Wu, Schatz, Lendvay, Fang, and Harding (WSLFH). We also studied the collinear H + Hz reaction by using the Liu-Siegbahn-Truhlar-Horowitz (LSTH) potential energy surface. The calculated thermal rate constant results were compared with reported values on the same surfaces. The success of these calculations demonstrates that time-independent vibrational configuration interaction can be a very convenient way to calculate converged quantum mechanical rate constants, and it opens the possibility of calculating converged rate constants for much larger reactions than have been treated until now.

Original languageEnglish (US)
Pages (from-to)6744-6749
Number of pages6
JournalProceedings of the National Academy of Sciences of the United States of America
Volume102
Issue number19
DOIs
StatePublished - May 10 2005
Externally publishedYes

Keywords

  • Chemical kinetics
  • Dynamics
  • Flux autocorrelation
  • Localized basis functions
  • Many-body problem

ASJC Scopus subject areas

  • General

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