Solving the Schrödinger equation with the free-complement chemical-formula theory: Variational study of the ground and excited states of Be and Li atoms.

Abstract

The chemical formula theory (CFT) proposed in Paper I of this series [H. Nakatsuji et al., J. Chem. Phys. 149, 114105 (2018)] is a simple variational electronic structure theory for atoms and molecules. The CFT constructs simple, conceptually useful wave functions for the ground and excited states, simultaneously, from the ground and excited states of the constituent atoms, reflecting the spirits of the chemical formulas. The CFT wave functions are also designed to be used as the initial wave functions of the free complement (FC) theory, that is, the exact theory producing the exact wave functions of the Schrödinger accuracy. This combined theory is referred to as the FC-CFT. We aim to construct an exact wave function theory that is useful not only quantitatively but also conceptually. This paper shows the atomic applications of the CFT and the FC-CFT. For simplicity, we choose the small atoms, Be and Li, and perform variational calculations to essentially exact levels. For these elements, a simple Hylleraas CI type formulation is known to be potentially highly accurate: we realize it with the CFT and the FC-CFT. Even from the CFT levels, the excitation energies to the Rydberg excited states were calculated satisfactorily. Then, with increasing the order of the FC theory in the FC-CFT, all the absolute energies and the excitation energies of the Be and Li atoms were improved uniformly and reached rapidly to the essentially exact levels in order 3 or 4 with moderately small calculational labors.