Electronic Structure and Geometry of NO2plus;and NO2minus;

摘要

The electronic structure of NO2plus;and NO2minus;has been investigated as a function of angle by means ofab initioMO LCAO SCF wavefunctions. Atomic orbitals used in the basis set are close to freehyphen;atom Hartreendash;Fock solutions. Several excited states, in addition to the ground states, have been obtained for the two ions. Total energies, population analyses, and onehyphen;electron orbital energies vs angle (Walsh diagrams) have been computed to aid interpretation of the wavefunctions. It turns out that the dramatic change in geometry from NO2plus;(linear) to NO2minus;(bent, 115.4deg;) can be understood by the occupancy and shape of a single orbital, the6a1in NO2minus;. Our results contribute to the establishment of a firm mathematical and numerical foundation of Walsh's rules and diagrams. The present calculations also serve to substantiate and extend previous wavefunctions for these important chemical species.