Use of scaled external correlation, a double many-body expansion, and variational transition state theory to calibrate a potential energy surface for FH2

Gillian C. Lynch, Rozeanne Steckler, David W. Schwenke, Antonio J C Varandas, Donald G. Truhlar, Bruce C. Garrett

Research output: Contribution to journalArticle

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Abstract

A new potential energy surface is presented for the reaction F + H 2 → HF + H. The regions of the surface corresponding to collinear and bent geometries in the F-H-H and H-F-H barrier regions are based on scaled external correlation (SEC) electronic structure calculations, and the F-H⋯H exit channel region is based on the previously developed surface No. 5. The functional form of the new surface includes dispersion forces by a double many-body expansion (DMBE), and the surface was adjusted so that the van der Waals well in the F⋯H-H region agrees with available experimental predictions. We have calculated stationary point properties for the new surface as well as product-valley barrier maxima of vibrationally adiabatic potential curves for F + H2 → HF(υ′ = 3) + H,F + HD-HF(υ′ = 3) + D, and F + D2 → DF(υ′ = 4) + D. The new surface should prove useful for studying the effect on dynamics of a low, early barrier with a wide, flat bend potential, as indicated by the best available electronic structure calculations.

Original languageEnglish (US)
Pages (from-to)7136-7149
Number of pages14
JournalThe Journal of Chemical Physics
Volume94
Issue number11
StatePublished - 1991
Externally publishedYes

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Potential energy surfaces
potential energy
expansion
Electronic structure
electronic structure
deuterium fluorides
valleys
Geometry
curves
products
geometry
predictions

ASJC Scopus subject areas

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

Cite this

Lynch, G. C., Steckler, R., Schwenke, D. W., Varandas, A. J. C., Truhlar, D. G., & Garrett, B. C. (1991). Use of scaled external correlation, a double many-body expansion, and variational transition state theory to calibrate a potential energy surface for FH2. The Journal of Chemical Physics, 94(11), 7136-7149.

Use of scaled external correlation, a double many-body expansion, and variational transition state theory to calibrate a potential energy surface for FH2. / Lynch, Gillian C.; Steckler, Rozeanne; Schwenke, David W.; Varandas, Antonio J C; Truhlar, Donald G.; Garrett, Bruce C.

In: The Journal of Chemical Physics, Vol. 94, No. 11, 1991, p. 7136-7149.

Research output: Contribution to journalArticle

Lynch, Gillian C. ; Steckler, Rozeanne ; Schwenke, David W. ; Varandas, Antonio J C ; Truhlar, Donald G. ; Garrett, Bruce C. / Use of scaled external correlation, a double many-body expansion, and variational transition state theory to calibrate a potential energy surface for FH2. In: The Journal of Chemical Physics. 1991 ; Vol. 94, No. 11. pp. 7136-7149.
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