Accurate scaling functions of the scaled Schrödinger equation

Abstract

The scaling function g of the scaled Schrödinger equation (SSE) is generalized to obtain accurate solutions of the Schrödinger equation (SE) with the free complement (FC) theory. The electron-nuclear and electron-electron scaling functions, g_iA and g_ij, respectively, are generalized. From the relations between SE and SSE at the inter-particle distances being zero and infinity, the scaling function must satisfy the collisional (or coalescent) condition and the asymptotic condition, respectively. Based on these conditions, general scaling functions are classified into "correct" (satisfying both conditions), "reasonable" (satisfying only collisional condition), and "approximate but still useful" (not satisfying collisional condition) classes. Several analytical scaling functions are listed for each class. Popular functions r_iA and r_ij belong to the reasonable class. The qualities of many electron-electron scaling functions are examined variationally for the helium atom using the FC theory. Although the complement functions of FC theory are produced generally from both the potential and kinetic operators in the Hamiltonian, those produced from the kinetic operator were shown to be less important than those produced from the potential operator. Hence, we used only the complement functions produced from the potential operator and showed that the correct-class g_ij functions gave most accurate results and the reasonable-class functions were less accurate. Among the examined correct and reasonable functions, the conventional function r_ij was worst in accuracy, although it was still very accurate. Thus, we have many potentially accurate "correct" scaling functions for use in FC theory to solve the SEs of atoms and molecules.