Electrical polarizability as a criterion for molecular wave functions

Abstract

Abstract A method is developed for obtaining the wave functions of homonuclear diatomic molecules. The method is a 'self-consistent’ one, since successive adjustments are made to the parameters in the wave function, making the calculated values of the electrical polarizability converge to the experimental ones. A preliminary discussion analyzes the influence of electron correlation and hybridization on polarizability, and the method is briefly applied to H+2 and H2, during which rules are found for using the self-consistent method. The major part of the paper is devoted to the study of the nitrogen molecule. The filled orbitals are represented by an orthonormal set which is constructed using the Schmidt process. The latter process enables much reduction to be made in the numerical computation. A full discussion is given of the various wave functions, most attention being given to the completely antisymmetric one. The π bonds in N2 are shown to have too great a longitudinal extension at large distances from the centre of the molecule, and this is empirically corrected by bringing closer together the atomic orbitals out of which the π bonds are made. Finally, the degrees of hybridization in the orbitals are given, and also the contributions which each orbital makes to the polarizability of the molecule.