Another Angle on Benchmarking Noncovalent Interactions.

For noncovalent interactions, the CCSD(T)-coupled cluster method is widely regarded as the "gold standard". With localized orbital approximations, benchmarks for ever larger complexes are being published, yet FN-DMC (fixed-node quantum Monte Carlo) intermolecular interaction energies diverge to a progressively larger degree from CCSD(T) as the system size grows, particularly when π-stacking is involved. Unfortunately, post-CCSD(T) methods like CCSDT(Q) are cost-prohibitive, which requires us to consider alternative means of estimating post-CCSD(T) contributions. In this work, we take a step back by considering the evolution of the correlation energy with respect to the number of subunits for such π-stacked sequences as acene dimers and alkadiene dimers. We show it to be almost perfectly linear and propose the slope of the line as a probe for the behavior of a given electron correlation method. By going further into the coupled cluster expansion and comparing with CCSDT(Q) results for benzene and naphthalene dimers, we show that CCSD(T) does slightly overbind but not as strongly as suggested by the FN-DMC results.