Explicit correlation and intermolecular interactions: Investigating carbon dioxide complexes with the CCSD(T)-F12 method

Abstract

We have optimized the lowest energy structures and calculated interaction energies for the CO₂–Ar, CO₂–N₂, CO₂–CO, CO₂–H₂O, and CO₂–NH₃ dimers with the recently developed explicitly correlated coupled cluster singles doubles and perturbative triples [CCSD(T)]-F12 methods and the associated VXZ-F12 (where X = D,T,Q) basis sets. For a given cardinal number, we find that results obtained with the CCSD(T)-F12 methods are much closer to the CCSD(T) complete basis set limit than the conventional CCSD(T) results. The relatively modest increase in the computational cost between explicit and conventional CCSD(T) is more than compensated for by the impressive accuracy of the CCSD(T)-F12 method. We recommend use of the CCSD(T)-F12 methods in combination with the VXZ-F12 basis sets for the accurate determination of equilibrium geometries and interaction energies of weakly bound electron donor acceptor complexes.