Electronic Structure of Hydrazoic Acid and the Azide Ion from X-Ray and Ultraviolet Electron Spectroscopy.

摘要

The electronic structures of hydrazoic acid and the azide ion have been investigated through the use of electron spectroscopy and quantum mechanical methods. Experimentally, the uv (He I and He II) electron spectra of gaseous HN3 and N2O and the X-ray (Al K alpha) electron spectra of the core and valance bands of NH3 frozen at 150 K and N3(-) in the form of solid LiN3 have been measured. Theoretically, results of INDO and ab initio MO calculations are used for spectral interpretation. Differential photoionization cross sections are calculated for the various photoelectron transitions and compared with the relative intensities of deconvoluted photoionization bands. The empirical potential model of Ellison is used for predicting nitrogen ls chemical shifts. The results of this investigation exemplify how the uv and X-ray electron spectroscopic techniques are symbiotic and how application of the two techniques along with the use of quantum mechanical methods can provide a complete and firm assignment of the occupied energy levels of a molecular system. Conclusions concerning the relative ionicity or degree of covalency of LiN3 and HN3 along with the decomposition mechanisms and products for HN3 are extracted from the experimental and computed results. (Author)