Interactions between large molecules pose a puzzle for reference quantum mechanical methods

Quantum-mechanical methods are used for understanding molecular interactions throughout the natural sciences. Quantum diffusion Monte Carlo (DMC) and coupled cluster with single, double, and perturbative triple excitations [CCSD(T)] are state-of-the-art trusted wavefunction methods that have been shown to yield accurate interaction energies for small organic molecules. These methods provide valuable reference information for widely-used semi-empirical and machine learning potentials, especially where experimental information is scarce. However, agreement for systems beyond small molecules is a crucial remaining milestone for cementing the benchmark accuracy of these methods. We show that CCSD(T) and DMC interaction energies are not consistent for a set of polarizable supramolecules. Whilst there is agreement for some of the complexes, in a few key systems disagreements of up to 8 kcal mol(-1) remain. These findings thus indicate that more caution is required when aiming at reproducible non-covalent interactions between extended molecules. Quantum-mechanical methods of benchmark quality are widely used for describing molecular interactions. The present work shows that interaction energies by CCSD(T) and DMC are not in consistent agreement for a set of polarizable supramolecules calling for cooperative efforts solving this conundrum.

Automated summary

Quantum-mechanical methods are widely employed for describing molecular interactions, but discrepancies between CCSD(T) and DMC interaction energies for a set of polarizable supramolecules call for further collaborative efforts to resolve this issue.