Weakest bound electron potential model theory

Abstract

AbstractDiffering from the self‐consistent field (SCF) method, in which an N‐electron atom problem is treated as a one‐electron problem with the use of a basic assumption of average potential, we develop a unified weakest bound electron potential model (WBEPM) theory. The relativistic form of the theory is given for the first time and is combined with the nonrelativistic form introduced in previous work to arrive at the unified WBEPM theory. The theory has two main ideas. First, from consideration of viewpoints of the dynamic successive ionization and the choice of zero of energy in quantum mechanics, an N‐electron atom system can be subdivided into N subsystems only containing a weakest bound electron (WBE) in each of subsystems. For each subsystem by separation of WBE and non‐weakest bound electrons (NWBE), WBE is believed to move in an approximate potential field provided by a “core” consisting of NWBEs and the nucleus. Thus, a complicated N‐electron problem is reduced to a simple analytical one‐electron problem of WBE. Second, the properties of an atom, such as total wave function, total energy, atomic energy levels, and transition between energy levels, can be investigated through the behaviors of a WBE or several WBEs, or up to all WBEs. Several excellent illustrative results show that the theory is capable of attaining very good computational accuracy. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2004