Benchmark calculations of some molecular properties of O2, CN and other selected small radicals using the ROHF-CCSD(T) method

Abstract

The capability of the ROHF-CCSD(T) method in obtaining accurate molecular properties in a defined and controlled way is analysed. Electron affinity, polarizability, and hyperpolarizability of the oxygen molecule in its ground state, electron affinity, electric dipole moment of the CN radical, and some other molecules serve as model cases for obtaining the ‘right result for the right reason’. Most calculated CCSD(T) data were extrapolated to the complete basis set (CBS) limit in order to minimize the basis set dependence of results. Some problems, specific to open shell systems include effects due to the spin adaptation, and details in the selection of the reference orbitals and related selection of denominators in non-iterative triples and other subtleties, which can affect the accuracy of the final ROHF-CCSD(T) results, are investigated.