Systematic discrepancies between reference methods for noncovalent interactions within the S66 dataset

Abstract

The accurate treatment of noncovalent interactions is necessary to model a wide range of applications, from molecular crystals to surface catalysts to aqueous solutions and many more. Quantum diffusion Monte Carlo (DMC) and coupled cluster theory with single, double, and perturbative triple excitations [CCSD(T)] are considered two widely trusted methods for treating noncovalent interactions. However, while they have been well-validated for small molecules, recent work has indicated that these two methods can disagree by more than 7.5 kcal/mol for larger systems. The origin of this discrepancy remains unknown. Moreover, the lack of systematic comparisons, particularly for medium-sized complexes, has made it difficult to identify which systems may be prone to such disagreements and the potential scale of these differences. In this work, we leverage the latest developments in DMC to compute interaction energies for the entire S66 dataset, containing 66 medium-sized complexes with a balanced representation of dispersion and electrostatic interactions. Comparison to previous CCSD(T) references reveals systematic trends, with DMC predicting stronger binding than CCSD(T) for electrostatic-dominated systems, while the binding becomes weaker for dispersion-dominated systems. We show that the relative strength of this discrepancy is correlated to the ratio of electrostatic and dispersion interactions, as obtained from energy decomposition analysis methods. Finally, we have pinpointed model systems: the hydrogen-bonded acetic acid dimer (ID 20) and dispersion-dominated uracil–cyclopentane dimer (ID 42), where these discrepancies are particularly prominent. These systems offer cost-effective benchmarks to guide future developments in DMC, CCSD(T), as well as the wider electronic structure theory community.