Quantum Monte Carlo benchmarking of large noncovalent complexes in the L7 benchmark set.

Abstract

We have used diffusion Monte Carlo (DMC) to perform calculations on the L7 benchmark set. DMC is a stochastic numerical integration scheme in real-space and part of a larger set of quantum Monte Carlo methods. The L7 set was designed to test the ability of electronic structure methods to include dispersive interactions. While the agreement between DMC and quantum-chemical state-of-the-art methods is excellent for some of the structures, there are significant differences in others. In contrast to wavefunction-based quantum chemical methods, DMC is a first-principle many-body method with the many-body wavefunction evolving in real space. It includes explicitly all electron-electron interactions and is relatively insensitive to the size of the basis set.