Benchmark full configuration-interaction calculations on HF and NH2

Abstract

Full configuration-interaction (FCI) calculations are performed at selected geometries for the 1-sigma(+) state of HF and the 2-B(1) and 2-A(1) states of NH2 using both DZ and DZP gaussian basis sets. Higher excitations become more important when the bonds are stretched and the self-consistent field (SCF) reference becomes a poorer zeroth-order description of the wave function. The complete active space SCF - multireference configuration-interaction (CASSCF-MRCI) procedure gives excellent agreement with the FCI potentials, especially when corrected with a multi-reference analog of the Davidson correction.