Electronic Structure and Electronic Spectrum of Nitrogen Dioxide: Study by the Nonempirical Self-Consistent Field Method

Publisher Website
Google Scholar
Abstract
The nonempirical self-consistent field method, in its form devised by McWeeny, has been applied to the ground state and to a series of excited states of nitrogen dioxide, using as basis functions Gaussians centered on the various atoms of the molecule. Potential-energy curves have been obtained by varying the bond angle; the resulting equilibrium bond angle for the ground state compares favorably well with the experimental value. It is found that five transitions fall into the range covered by the long-wavelength spectrum, which explains the complexity of the latter. From the correlations between the electronic states of the bent molecule and those of the linear system, an attempt is made to obtain indications concerning the potential-energy surfaces of the NO+O system. Finally, the significance of the potential-energy diagram obtained is discussed in relation with two problems: the mechanism of the photolysis of the compound, and the anomalously long radiative lifetime of its first doublet excited state resulting from fluorescence decay.

This publication has 32 references indexed in Scilit: