Combined quantum Monte Carlo – effective fragment molecular orbital method: fragmentation across covalent bonds

Abstract

The previously developed combined Quantum Monte Carlo-Effective Fragment Molecular Orbital (QMC-EFMO) method is extended to systems in which the fragmentation process cuts across covalent molecular bonds. The extended QMC-EFMO capability is demonstrated on a few model systems: the glycine tetramer, the diglycine reaction to form a dipeptide, silica-based rings, and polyalanine chains of increasing length. The agreement between full QMC and QMC-EFMO for the correlation energy is within 2 kcal mol⁻¹ and for the correlation energy differences is within 1 kcal mol⁻¹.