Frozen core approximation, a pseudopotential method tested on six states of NaH

Abstract

A pseudopotential formulation, more appropriately called the frozen core approximation (FCA), is presented in detail. This FCA is tested by performing MCSCF calculations on the six low lying states, X1Σ+, A1Σ+, a3Σ+, c3Σ+, B1Π, and b3Π of NaH. The results obtained are compared with those of an analogous previous MCSCF calculation on these states without the use of FCA, i.e., with all orbitals optimized. It is found that energies are obtained rather accurately with FCA; however, calculated molecular properties are affected more strongly and the shapes of the potential curves appear to be distorted somewhat by FCA. It is argued that no pseudo- or model-potential calculation can give errors less than FCA unless the potential is made valence shell dependent. This, however, would be analogous to a full calculation, and the savings due to a pseudopotential approximation would be lost.