Infrared Absorption Spectra of t‐HNOH Radicals Generated on VUV Irradiation of NO in Solid Hydrogen

Abstract

Photoproduct signature: Irradiation of solid hydrogen near 3 K containing NO with vacuum-UV light from synchrotron radiation yields new infrared absorption lines at 1241.7, 1063.6 and 726.2 cm(-1) (see figure). These new lines are assigned to vibrational modes of t-HNOH. This photoproduct is formed from electronically excited NO reacting with neighboring hydrogen in the solid sample.Irradiation of solid H(2) near 3 K containing NO with vacuum-ultraviolet light from a synchrotron yields new infrared absorption lines at 1241.7, 1063.6 and 726.2 cm(-1). The structures of four possible structural isomers: H(2)NO, t-HNOH, c-HNOH and NOH(2), their vibrational wavenumbers, IR intensities and D-isotopic shifts are calculated with density-functional theory according to B3LYP and PW91PW91/aug-cc-pVTZ methods. Based on the results of those calculations and of experiments with deuterium labeling, we assign the new lines to nu(4) (cis bending), nu(5) (N==O stretching) and nu(6) (out-of-plane deformation) modes, respectively, of t-HNOH. This photoproduct is formed through reaction of electronically excited NO with neighboring H(2) in the solid sample.