The ultraviolet absorption spectrum of the <i>A</i> 1<i>A</i>″2←<i>X</i> 1<i>A</i>1 transition of jet-cooled ammonia

Abstract

The Ã←X̃ absorption spectra of NH3 and ND3, recorded in a cold molecular jet, are presented. Vibrational band progressions resolvable up to v′2=14 appear. No other vibrations are present, either alone or in combinations. Relative band intensities for v2 progressions are recorded, and the homogeneous lifetime broadenings of vibrational levels of the à state are reported. The FWHM linewidths span 34–293 cm−1 over all bands of NH3 and 30–135 cm−1 over the v′2=2 through 14 bands of ND3. In general, the rate of dissociation increases nonlinearly with vibrational energy. The band intensity alternation, previously observed only in matrix spectra below 15 K, has been observed in these very cold gas phase samples.