The Photolysis of Matrix Isolated cis-Thionylimide. 1. The Identification and Infrared Spectra of cis-HOSN, HSNO, and SNO

Abstract

PETER 0 . TCHIR and RICHARD D. SPRATLEY. Can. J . Chem. 53,2318Chem. 53, (1975. cis-HNSO has been photolyzed in argon matrices using a medium pressure mercury lamp. Examination of the infrared spectra has revealed the presence of four photolysis products. With the aid of isotopic substitution these species have been identfied as cis-HOSN, cis-HSNO, trans-HSNO, and SNO, all previously unknown. Assignments have been made for a11 four products and force fields calculated for cis-HOSN and trans-HSNO. The following reaction scheme has been postulated for the photolysis induced process: cis-HNSO -+ cis-HOSN -+ cis-HSNO + trans-HSNO -+ SNO. The extent of this reaction sequence has been found to depend on reaction time and photolysis energy. IntroductionIn the ultraviolet spectrum of cis-HNSO only one diffuse absorption and one continuum were observed (1). From this observation it was deduced that photolysis of the molecule was occurring. Since it was possible that the hydrogen was being removed to give the NSO radical, this photolysis appeared to be an ideal system for a study utilizing the matrix isolation technique. In this technique a hydrogen atom can diffuse away through the matrix to leave behind the isolated, stabilized radical. On the other hand, if the product or products were unstable isomers of cis-HNSO, they might also be stabilized at the low temperature of the matrix.In this paper we describe the results of the mercury arc photolysis of cis-HNSO in argon matrices: in part I the infrared results are presented and four new molecular species are identified; in part I1 the reactions taking place in the matrix are considered.

On the Detectability of the HSS, HSO, and HOS Radicals in the Interstellar Medium

“…Even so, sulfur is one of the eleven elements that appear on the astrochemist's periodic table (McCall 2006), and is present in many known interstellar molecules (Penzias et al 1971;Gottlieb & Ball 1973;Fock & McAllister 1982;McCarthy & Thaddeus 2001;Tercero et al 2010;Neufeld et al 2012;Gratier et al 2016). It is necessary to life as we know it, gives rise to novel chemistry in extreme environments like hot springs and black smokers on Earth, heavily influences the atmospheric chemistry of Venus (Krasnopolsky 2007(Krasnopolsky , 2012 as well as the surface chemistry of Io, and is present in various terrestrial pollutants (Tchir & Spratley 1975;Hawkins & Downs 1984). Consequently, sulfur cannot be neglected for astrochemical analysis, and an understanding for its importance in the chemistry of space has been continually growing since various molecular sulfur detections began in the 1970s (Morris et al 1975;Henkel et al 1983;Johansson et al 1984;Ziurys et al 1984;Cernicharo et al 1987Cernicharo et al , 2000Kaifu et al 1987;Saito et al 1987;Turner 1987Turner , 1992Kahane et al 1988;Martín-Pintado et al 1992;Boyle et al 1994;Turner et al 1998;Schilke et al 2001Schilke et al , 2003Mauersberger et al 2004;Sakai et al 2007;Finney et al 2016).…”

Analysis of the High-Resolution Fourier Transform Infrared Spectra of the ν3and ν5Bands of Thionylimide (HNSO)

“…Photochemical studies of HNSO in matrices have detected absorption lines due to residual water vapor in the spectrometer. the formation of NSO, SNO, and various HNSO isomers (15,16).…”

Photoelectron spectroscopy of the thiazate (NSO−) and thionitrite (SNO−) isomer anions

“…13 18 A common theme of these studies is that SNO or NSO were observed as a decomposition product of other S, N, and O containing molecules. Early assignments of the stretching vibrational frequencies of SNO and NSO came from Tchir and Sprately, 13,14 where isomers of HSNO were formed in an argon matrix and subsequent UV irradiation yielded several vibrational absorption peaks. Some of these peaks were then attributed to either SNO or NSO, resulting in an assignment of the NO stretch and SNO bend vibrational frequencies of SNO 13 and the SO stretching frequency for NSO.…”

“…Early assignments of the stretching vibrational frequencies of SNO and NSO came from Tchir and Sprately, 13,14 where isomers of HSNO were formed in an argon matrix and subsequent UV irradiation yielded several vibrational absorption peaks. Some of these peaks were then attributed to either SNO or NSO, resulting in an assignment of the NO stretch and SNO bend vibrational frequencies of SNO 13 and the SO stretching frequency for NSO. 14 It was later suggested that the initial assignments of SNO vibrational frequencies were better matched to the SN and NO stretches, rather than the NO stretch and SNO bend.…”