Basis set limit coupled-cluster studies of hydrogen-bonded systems

Abstract

As hydrogen-bonded systems are of utmost importance in especially biological and chemical systems, a new set of highly accurate reference dissociation energies, denoted HB49, is devised. For the molecules in this set, the basis set convergence of post-Hartree–Fock methods, including F12 methods, is investigated. Using combined Møller–Plesset perturbation theory (MP2) and CCSD(T) approaches for energies and MP2 and QCISD(T) for gradients, we achieve CCSD(T) accuracy, which has been determined before to yield an accuracy of 0.2 kJ/mol for a subset of HB49. Both conventional extrapolation techniques and F12 techniques are competitive with each other. By using MP2+ΔCCSD(T), a rather fast basis set convergence is obtained when both basis sets are carefully chosen.