A new potential energy surface for vibration-vibration coupling in HF-HF collisions. Formulation and quantal scattering calculations

David W. Schwenke, Donald G. Truhlar

Research output: Contribution to journalArticle

28 Scopus citations

Abstract

We present new ab initia calculations of the HF-HF interaction potential for the case where both molecules are simultaneously displaced from their equilibrium internuclear distance. These and previous ab initio calculations are then fit to a new analytic representation which is designed to be efficient to evaluate and to provide an especially faithful account of the forces along the vibrational coordinates. We use the new potential for two sets of quantal scattering calculations for collisions in three dimensions with total angular momentum zero. First we test that the angular harmonic representation of the anisotropy is adequate by comparing quantal rigid rotator calculations to those carried out for potentials involving higher angular harmonics and for which the expansion in angular harmonics is systematically increased to convergence. Then we carry out large-scale quantal calculations of vibration-vibration energy transfer including the coupling of both sets of vibrational and rotational coordinates. These calculations indicate that significant rotational energy transfer accompanies the vibration-to-vibration energy transfer process.

Original languageEnglish (US)
Pages (from-to)4800-4813
Number of pages14
JournalThe Journal of chemical physics
Volume88
Issue number8
DOIs
StatePublished - Jan 1 1988

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