Benchmark full configuration-interaction calculations on H2O, F, and F−

Abstract

Full configuration-interaction calculations are reported, and compared to other methods, for H2O at its equilibrium geometry and at two geometries with the H–O bonds stretched. Since the percentage of the SCF reference in the FCI wave function decreases greatly with the bond elongation, the accuracy of techniques based on a single reference do not compare well with the FCI results. However, the results from a CASSCF/MRCI treatment are in good agreement with the FCI. Correlation effects in F compared to Ne are far more similar than for F− compared to Ne, despite F− and Ne being isoelectronic. Since the importance of higher than double excitations is greater for F− than F, a very high percentage of the correlation must be obtained to accurately compute the electron affinity. In a CASSCF/MRCI treatment the higher than quadruple excitations contribute 0.02 eV to the E.A., even for modest basis sets.