Assessment of Weak Intermolecular Interactions Across QM/MM Noncovalent Boundaries

An assessment of a number of quantum mechanical/molecular mechanical (QM/MM) combinations was performed for weak intermolecular interactions across noncovalent QM/MM 'boundaries'. The popular S22 data set, comprising of a number of weak hydrogen-bonded, dispersion-bound and complexes with mixed interactions was used for the assessment. A range of QM methods was combined with a number of popular MM force fields. The single-point interaction energies, at reference geometries, are presented as deviations to accurate CCSD(T)/CBS reference values. This investigation employed both additive and subtractive QM/MM schemes. The density functional has only a negligible effect; the choice of basis set was also negligible in terms of accuracy. The importance of selecting the most appropriate MM force field for accurately describing interactions at the noncovalent 'boundary' region has a dramatic effect on the accuracy.