Functional Representation for the Born-Oppenheimer Diagonal Correction and Born-Huang Adiabatic Potential Energy Surfaces for Isotopomers of H3

被引:32
作者
Mielke, Steven L. [1 ]
Schwenke, David W. [2 ]
Schatz, George C. [1 ]
Garrett, Bruce C. [3 ]
Peterson, Kirk A. [4 ]
机构
[1] Northwestern Univ, Dept Chem, Evanston, IL 60208 USA
[2] NASA, Ames Res Ctr, Moffett Field, CA 94035 USA
[3] Pacific NW Natl Lab, Chem & Mat Sci Div, Richland, WA 99352 USA
[4] Washington State Univ, Dept Chem, Pullman, WA 99164 USA
关键词
TRANSITION-STATE THEORY; MECHANICAL REACTIVE SCATTERING; ATOM TRANSFER-REACTIONS; WAVE-FUNCTIONS; VARIATIONAL METHOD; HYDROGEN MOLECULE; H+H-2 REACTION; BASIS-SETS; APPROXIMATION; DYNAMICS;
D O I
10.1021/jp8110887
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Multireference configuration interaction (MRCI) calculations of the Born-Oppenheimer diagonal correction (BODC) for H-3 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 H-3, DH2, and MuH(2) 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 (similar to 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.
引用
收藏
页码:4479 / 4488
页数:10
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