ISSN print edition: 0366-6352 ISSN electronic edition: 1336-9075 Registr. No.: MK SR 9/7 Published monthly

Maximum overlap approximation calculations on polyatomic molecules. III. Nature of the maximum overlap criterion

R. Boča, P. Pelikán, and L. Valko

Department of Inorganic Chemistry, Slovak Technical University, 880 37 Bratislava

Abstract: The nature of the max. overlap criterion fr choice of optimum hybrid AOs (HAOs) was analyzed. Using the quantum-mech. virial theorem the mol. binding energy on MO LCHAO level of approxn. through kinetic integrals was expressed. As the kinetic integrals for STO can be expressed in terms of overlap integrals, the maximization of the mol. binding energy corresponds to the maximization of a weighted sum of overlap integrals. Semiempirical weighted parameters K which secure the reprodn. of the total mol. binding energy are transferable in a good approxn. from one mol. to another. Binding energies for nine halomethanes using six different basis sets of AOs are perfect reproduced.

Full paper in Portable Document Format: 333a289.pdf

Chemical Papers 33 (3) 289–299 (1979)