
doi: 10.1063/1.3377091
pmid: 20441261
We present a technique for using quantum Monte Carlo (QMC) to obtain high quality energy differences. We use generalized valence bond (GVB) wave functions, for an intuitive approach to capturing the important sources of static correlation, without needing to optimize the orbitals with QMC. Using our modifications to Walker branching and Jastrows, we can then reliably use diffusion quantum Monte Carlo to add in all the dynamic correlation. This simple approach is easily accurate to within a few tenths of a kcal/mol for a variety of problems, which we demonstrate for the adiabatic singlet-triplet splitting in methylene, the vertical and adiabatic singlet-triplet splitting in ethylene, 2+2 cycloaddition, and Be2 bond breaking.
VB calculations, wave functions, triplet state, Monte Carlo methods, quantum theory, 540, bonds (chemical), organic compounds, 530
VB calculations, wave functions, triplet state, Monte Carlo methods, quantum theory, 540, bonds (chemical), organic compounds, 530
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