All-pair wave function and reduced variational equation for electronic systems

✍ Scribed by G. Náray-Szabó

• Publisher: John Wiley and Sons
• Year: 1975
• Tongue: English
• Weight: 521 KB
• Volume: 9
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/qua.560090103

✦ Synopsis

Abstract

A new type of wave function is proposed for atomic and molecular systems. This all‐pair function is constructed of N(N – 1)/2 identical geminals for N electrons. For systems with the highest multiplicity this is the full space part of the wave function. For closed shell systems it has to be multiplied by a Slater determinant according to the antisymmetry condition. In the case of maximal multiplicity a reduced variational equation is derived for the geminal. This equation is independent of the dimensionality of the system and contains the particle number as a multiplicative factor only. The method is extended to the closed shell case where a restriction has to be fulfilled. The reduction of the variational equation can be done only approximately. The use of identical geminals can be treated as a first approximation. An extension of the method, called the pair interdependent configuration interaction (PICI), is proposed. The special features of the method are discussed briefly.