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The Breathing Orbital Valence Bond Method in Diffusion Monte Carlo: C-H Bond Dissociation ofAcetylene

Journal Article · · American Chemical Society
DOI:https://doi.org/10.1021/jp8020062· OSTI ID:948130
This study explores the use of breathing orbital valence bond (BOVB) trial wave functions for diffusion Monte Carlo (DMC). The approach is applied to the computation of the carbon-hydrogen (C-H) bond dissociation energy (BDE) of acetylene. DMC with BOVB trial wave functions yields a C-H BDE of 132.4 {+-} 0.9 kcal/mol, which is in excellent accord with the recommended experimental value of 132.8 {+-} 0.7 kcal/mol. These values are to be compared with DMC results obtained with single determinant trial wave functions, using Hartree-Fock orbitals (137.5 {+-} 0.5 kcal/mol) and local spin density (LDA) Kohn-Sham orbitals (135.6 {+-} 0.5 kcal/mol).
Research Organization:
Ernest Orlando Lawrence Berkeley National Laboratory, Berkeley, CA (US)
Sponsoring Organization:
Chemical Sciences Division
DOE Contract Number:
AC02-05CH11231
OSTI ID:
948130
Report Number(s):
LBNL-1466E
Journal Information:
American Chemical Society, Journal Name: American Chemical Society Journal Issue: 38 Vol. 112
Country of Publication:
United States
Language:
English

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