A global H2O potential energy surface for the reaction O(1D) + H2→OH+H

Tak San Ho, Timothy Hollebeek, Herschel Rabitz, Lawrence B. Harding, George C Schatz

Research output: Contribution to journalArticle

168 Citations (Scopus)

Abstract

A global, single-valued ground-state H2O potential surface for the reaction O(1D) + H2→OH+H has been constructed from a new set of accurate ab initio data using a general multidimensional interpolation method. The ab initio calculations are of the multireference, configuration interaction variety and were carried out using augmented polarized triple zeta basis sets. The multidimensional method is formulated within the framework of the reproducing kernel Hubert space theory. The H2O potential is expressed as a many-body sum of a single one-body term, three two-body terms, and a single three-body term. The one-body term is the dissociation energy to the three-atom limit 2H(2S) + O(3P). The two-body terms are two O-H and one H-H adiabatic diatomic potentials of lowest energy. Each diatomic term is obtained by interpolating a discrete set of ab initio data using a one-dimensional, second-order, distancelike reproducing kernel. The three-body term is obtained by interpolating the difference of the H2O ab initio data and the one- and two-body sum by means of a direct product of three one-dimensional reproducing kernels on an optimized regular three-dimensional grid. The H2O potential energy surface is accurate, globally smooth, easy to evaluate, and asymptotically correct. Extensive quasiclassical trajectory calculations based on this new potential energy surface have been performed and compared with the results based on the potential energy surface of Murrell and Carter (MC) and that of Schinke and Lester (SL). Comparisons with recent experimental measurements on total cross sections, isotope effects, rate constants, vibrational, rotational, and angular distributions of the O(1D) + H2/HD reaction show that the new potential enerev surface is a significant improvement over the MC and SL surfaces.

Original languageEnglish
Pages (from-to)10472-10486
Number of pages15
JournalJournal of Chemical Physics
Volume105
Issue number23
Publication statusPublished - 1996

Fingerprint

Potential energy surfaces
potential energy
Angular distribution
Isotopes
Ground state
Rate constants
Interpolation
Trajectories
Atoms
isotope effect
configuration interaction
interpolation
angular distribution
grids
trajectories
dissociation
ground state
energy
cross sections

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Ho, T. S., Hollebeek, T., Rabitz, H., Harding, L. B., & Schatz, G. C. (1996). A global H2O potential energy surface for the reaction O(1D) + H2→OH+H. Journal of Chemical Physics, 105(23), 10472-10486.

A global H2O potential energy surface for the reaction O(1D) + H2→OH+H. / Ho, Tak San; Hollebeek, Timothy; Rabitz, Herschel; Harding, Lawrence B.; Schatz, George C.

In: Journal of Chemical Physics, Vol. 105, No. 23, 1996, p. 10472-10486.

Research output: Contribution to journalArticle

Ho, TS, Hollebeek, T, Rabitz, H, Harding, LB & Schatz, GC 1996, 'A global H2O potential energy surface for the reaction O(1D) + H2→OH+H', Journal of Chemical Physics, vol. 105, no. 23, pp. 10472-10486.
Ho, Tak San ; Hollebeek, Timothy ; Rabitz, Herschel ; Harding, Lawrence B. ; Schatz, George C. / A global H2O potential energy surface for the reaction O(1D) + H2→OH+H. In: Journal of Chemical Physics. 1996 ; Vol. 105, No. 23. pp. 10472-10486.
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