Density matrix averaged atomic natural orbital (ANO) basis sets for correlated molecular wave functions

Summary

Generally contracted basis sets for first row atoms have been constructed using the Atomic Natural Orbital (ANO) approach, with modifications for allowing symmetry breaking and state averaging. The ANOs are constructed by averaging over several atomic states, positive and negative ions, and atoms in an external electric field. The contracted basis sets give virtually identical results as the corresponding uncontracted sets for the atomic properties, which they have been designed to reproduce. The design objective has been to describe the ionization potential, the electron affinity, and the polarizability as accurately as possible. The result is a set of well-balanced basis sets for molecular calculations. The starting primitive sets are 8s4p3d for hydrogen, 9s4p3d for helium, and 14s9p4d3f for the heavier first row atoms.