General Theory of Spin-Coupled Wave Functions for Atoms and Molecules

Publisher Summary This chapter focuses on a spin-coupled wavefunction theory, examining its consequences for the understanding of the electronic structure of atoms and molecules pursued at some length. One of the most important features of the theory is the great flexibility imparted to it by the use of many different bases of spin functions. The transformations between such bases provide a useful insight into some of the processes that occur when a chemical bond is formed. In addition, this formulation makes it possible to discuss both the equilibrium properties of molecules and their dissociation into atoms within the same framework. The theory would also then be directly applicable to a much larger class of molecules. The symmetries of the orbitals concerned play a central role in such approximate treatments, because these essentially determine which overlaps may be reasonably neglected and which may not.

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