Fixed-node diffusion Monte Carlo study of the structures of m-benzyne

TL;DR

This study uses diffusion Monte Carlo methods with optimized trial wave functions to accurately determine the equilibrium structures of m-benzyne, confirming the monocyclic form as more stable than the bicyclic form.

Contribution

It applies advanced DMC techniques with reoptimized multi-configuration trial wave functions to accurately compare the structures of m-benzyne.

Findings

Monocyclic structure is lower in energy by 1.9 kcal/mole.

Results agree with high-level coupled cluster calculations.

Demonstrates effectiveness of DMC with reoptimized trial wave functions.

Abstract

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.