Transposition of the Theories Describing Superconducting Systems to Molecular Systems. Method of Biorbitals

摘要

A new theory of the electronic structure of molecules is proposed, based on a wavefunction of the following type:phgr;SCFminus;BIequals;NApsgr;lpar;1,2rpar;psgr;lpar;3,4rpar;middot;middot;middot;psgr;lpar;2Nmiddot;middot;middot;1,2Nrpar;.This wavefunction is called the selfhyphen;consistenthyphen;field biorbital wavefunction, and the factors psgr;(i, j) are called biorbitals. This function is discussed, the corresponding energy expression is derived, and the variational equations leading to the best possible phgr;SCFsngbnd;BIare presented. This theory is the molecular version of Blatt's theory of superconducting systems.