Diffusion Monte Carlo (DMC) calculations are performed on the monocyclic and bicyclic forms of m-benzyne, which are the equilibrium structures at the CCSD(T) and CCSD levels of coupled cluster theory. We employed multi-configuration self-consistent field trial wave functions which are constructed from a carefully selected 8-electrons-in-8-orbitals complete active space [CAS(8,8)], with CSF coefficients that are reoptimized in the presence of a Jastrow factor. The DMC calculations show that the monocyclic structure is lower in energy than the bicyclic structure by 1.9(2) kcal/mole, in excellent agreement with the best coupled cluster results.
@article{arxiv.0803.0946,
title = {Fixed-node diffusion Monte Carlo study of the structures of m-benzyne},
author = {W. A. Al-Saidi and C. J. Umrigar},
journal= {arXiv preprint arXiv:0803.0946},
year = {2009}
}