Isomers of HSCO: IR absorption spectra of t-HSCO in solid Ar.
Irradiation of an Ar matrix sample containing H2S and CO (or OCS) with an ArF excimer laser at 193 nm yields trans-HSCO (denoted t-HSCO). New lines at 1823.3, 931.6, and 553.3 cm(-1) appear after photolysis and their intensity enhances after annealing; secondary photolysis at 248 nm diminishes these lines and produces OCS and CO. These lines are assigned to C-O stretching, HSC-bending, and C-S stretching modes of t-HSCO, respectively, based on results of 13C-isotopic experiments and theoretical calculations. Theoretical calculations using density-functional theories (B3LYP and PW91PW91) predict four stable isomers of HSCO: t-HSCO, c-HSCO, HC(O)S, and c-HOCS, listed in increasing order of energy. According to calculations with B3LYP/aug-cc-pVTZ, t-HSCO is planar, with bond lengths of 1.34 A (H-S), 1.81 A (S-C), and 1.17 A (C-O), and angles angle HSC congruent with 93.4 degrees and angle SCO congruent with 128.3 degrees; it is more stable than c-HSCO and HC(O)S by approximately 9 kJ mol(-1) and more stable than c-HOCS by approximately 65 kJ mol(-1). Calculated vibrational wave numbers, IR intensities, and 13C-isotopic shifts for t-HSCO fit satisfactorily with experimental results. This new spectral identification of t-HSCO provides information for future investigations of its roles in atmospheric chemistry.
Lo
Wen-Jui
WJ
Department of Nursing, Tzu Chi College of Technology, Hualien 970, Taiwan. wjll@tccn.edu.tw
Chen
Hui-Fen
HF
Wu
Yu-Jong
YJ
Lee
Yuan-Pern
YP
D002247:Carbon Isotopes / Q000737:chemistry; D002248:Carbon Monoxide / Q000737:chemistry*; D006862:Hydrogen Sulfide / Q000737:chemistry*; D007536:Isomerism; D008962:Models, Theoretical; D010777:Photochemistry; D010782:Photolysis; D013055:Spectrophotometry, Infrared / Q000379:methods*; D013816:Thermodynamics; D014732:Vibration
D002247:Carbon Isotopes; D002248:Carbon Monoxide; D006862:Hydrogen Sulfide