The Stereochemical Consequences of Coulomb Polarization in Ground State Molecules
In the original monograph,1 we distinguished five different types of MOVB interaction matrix elements shown in Figure 1. In previous chapters, we have focused primary attention on the chemical implications of CT interaction and we have also seen what role bielectronic polarization plays in problems of molecular electronic structure, with the confines of VB and MOVB theory. Our intention now is to rationally design systems in which monoelectronic polarization and bielectronic correlation becomes as important as CT interaction and probe the stereochemical consequences of CW interaction brought about by the pij and Wij interaction matrix elements. For reasons that will become apparent, we shall refer to bonding effected by the pij and Wij. matrix elements as coulomb polarization refering to the specific mechanisms as either p or W polarization. For pedagogical reasons, we develop the theory of p and W polarization using elementary systems from which we ultimately generalize to the polyelectronic species. As we shall see, coulomb polarization becomes important when the constituent atoms of a system are weak overlap binders. Thus, this is yet another dimension of the general problem of weak binding first discussed in chapters 1 and 2.
KeywordsInteraction Matrix Element Molecular Electronic Structure Ground State Molecule Fragment Orbital Ligand Fragment
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