Gaussian functions with odd power of r produced by the free complement theory.

Abstract

We investigate, in this paper, the Gaussian (G) function with odd powers of r, rxaybzcexp(-αr2), called the r-Gaussian or simply the rG function. The reason we investigate this function here is that it is generated as the elements of the complement functions (cf's) when we apply the free complement (FC) theory for solving the Schrödinger equation to the initial functions composed of the Gaussian functions. This means that without the rG functions, the Gaussian set of functions cannot produce the exact solutions of the Schrödinger equation, showing the absolute importance of the rG functions in quantum chemistry. Actually, the rG functions drastically improve the wave function near the cusp region. This was shown by the applications of the present theory to the hydrogen and helium atoms. When we use the FC-sij theory, in which the inter-electron function rij is replaced with its square sij=rij2 that is integrable, we need only one- and two-electron integrals for the G and rG functions. The one-center one- and two-electron integrals of the rG functions are always available in a closed form. To calculate the integrals of the multi-centered rG functions, we proposed the rG-NG expansion method, in which an rG function is expanded by a linear combination of the G functions. The optimal exponents and coefficients of this expansion were given for N = 2, 3, 4, 5, 6, and 9. To show the accuracy and the usefulness of the rG-NG method, we applied the FC-sij theory to the hydrogen molecule.