Functional representation for the born-oppenheimer diagonal correction and born-huang adiabatic potential energy surfaces for isotopomers of H3

Steven L. Mielke, David W. Schwenke, George C Schatz, Bruce C. Garrett, Kirk A. Peterson

Research output: Contribution to journalArticle

30 Citations (Scopus)

Abstract

Multireference configuration interaction (MRCI) calculations of the Born-Oppenheimer diagonal correction (BODC) for H3 were performed at 1397 symmetry-unique configurations using the Handy-Yamaguchi-Schaefer approach; isotopic substitution leads to 4041 symmetry-unique configurations for the DH2 mass combination. These results were then fit to a functional form that permits calculation of the BODC for any combination of isotopes. Mean unsigned fitting errors on a test grid of configurations not included in the fitting process were 0.14, 0.12, and 0.65 cm-1 for the H3,DH2, and MuH2 isotopomers, respectively. This representation can be combined with any Born-Oppenheimer potential energy surface (PES) to yield Born-Huang (BH) PESs; herein, we choose the CCI potential energy surface, the uncertainties of which (∼0.01 kcal/mol) are much smaller than the magnitude of the BODC. Fortran routines to evaluate these BH surfaces are provided. Variational transition state theory calculations are presented comparing thermal rate constants for reactions on the BO and BH surfaces to provide an initial estimate of the significance of the diagonal correction for the dynamics.

Original languageEnglish
Pages (from-to)4479-4488
Number of pages10
JournalJournal of Physical Chemistry A
Volume113
Issue number16
DOIs
Publication statusPublished - Apr 23 2009

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Potential energy surfaces
potential energy
configurations
Isotopes
Rate constants
symmetry
Substitution reactions
configuration interaction
isotopes
grids
substitutes
estimates

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

Cite this

Functional representation for the born-oppenheimer diagonal correction and born-huang adiabatic potential energy surfaces for isotopomers of H3. / Mielke, Steven L.; Schwenke, David W.; Schatz, George C; Garrett, Bruce C.; Peterson, Kirk A.

In: Journal of Physical Chemistry A, Vol. 113, No. 16, 23.04.2009, p. 4479-4488.

Research output: Contribution to journalArticle

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AU - Peterson, Kirk A.

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