On Physical Properties and Interactions of Polyatomic Molecules: With Application to Molecular Recognition in Biology

Publisher Summary This chapter evaluates the properties of semiempirical all-valence-electron molecular orbital theory for description of the charge distribution of polyatomic molecules. The chapter focuses on two of important methods, that is, the iterative extended Huckel theory (IEHT) method and the complete neglect of differential overlap (CNDO) method. The formal treatment of intermolecular forces is based on quantum mechanical perturbation theory. The analysis of wave functions aims to establish the relative usefulness of the two types of wave functions in predicting values for various physical properties. It determines the particular electronic aspects to which a given type of wave function is most sensitive and thereby evaluates the relative applicability of these wave functions to the various physical problems under study. The dipole approximation for short separation distances and for molecules of the size and complexity of pyridine is inadequate and the monopole approximation fails for all considered separation distances. The theory of electronic structure and intermolecular interactions is applied to molecular biology that is the characterization of the nature of physical interactions involved in molecular recognition processes. Electrostatic interactions play a fundamental role in molecular recognition processes. The development of quantitative treatment for these interactions makes possible an unambiguous evaluation of the degree to which these interactions participate in such fundamental biological events as hydrogen bonding formation and stability, and enzyme-substrate interactions.

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