Generalized valence bond wave functions in quantum Monte Carlo.
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 Be(2) bond breaking.
Anderson
Amos G
AG
Materials and Process Simulation Center, Division of Chemistry and Chemical Engineering, California Institute of Technology, (MC 139-74) Pasadena, California 91125, USA. amosa@alumni.caltech.edu
Goddard
William A
WA