Theoretical reference values for the AE6 and BH6 test sets from explicitly correlated coupled-cluster theory

Abstract

We propose a new computational protocol to obtain highly accurate theoretical reference data. This protocol employs the explicitly correlated coupled-cluster method with iterative single and double excitations as well as perturbative triple excitations, CCSD(T)(F12), using quadruple-\(\zeta\) basis sets. Higher excitations are accounted for by conventional CCSDT(Q) calculations using double-\(\zeta\) basis sets, while core/core-valence correlation effects are estimated by conventional CCSD(T) calculations using quadruple-\(\zeta\) basis sets. Finally, scalar-relativistic effects are accounted for by conventional CCSD(T) calculations using triple-\(\zeta\) basis sets. In the present article, this protocol is applied to the popular test sets AE6 and BH6. An error analysis shows that the new reference values obtained by our computational protocol have an uncertainty of less than 1 kcal/mol (chemical accuracy). Furthermore, concerning the atomization energies, a cancellation of the basis set incompleteness error in the CCSD(T)(F12) perturbative triples contribution with the corresponding error in the contribution from higher excitations is observed. This error cancellation is diminished by the CCSD(T*)(F12) method. Thus, we recommend the use of the CCSD(T*)(F12) method only for small- and medium-sized basis sets, while the CCSD(T)(F12) approach is preferred for high-accuracy calculations in large basis sets.