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Infrared spectra of HSCS + , c-HSCS, and HCS 2 - produced on electron bombardment of CS 2 in solid para-hydrogen.

We report infrared (IR) spectra of HSCS+ , c-HSCS, HCS2 - , and other species produced on electron bombardment of a mixture of CS2 and para-hydrogen (p-H2 ) during deposition at 3.2 K. After maintenance of the deposited matrix in darkness for 12 h, the intensities of the absorption lines of HSCS+ at 2477.2 (ν1 ), 1525.6 (ν2 ), and 919.6 cm-1 (ν3 ) decreased through neutralization of HSCS+ with trapped electrons. During this period, the intensities of the lines of HCS2 - at 2875.7 (ν1 ), 1249.9 (ν5 ), 1003.2 (ν6 ), and 814.3 cm-1 (ν4 ) increased due to reaction between H and CS2 - . The intensities of the lines observed at 2312.7 and 889.0 cm-1 , which are assigned to the c-HSCS radical, increased after maintenance in darkness and greatly diminished after irradiation at 373 nm. The IR spectra of HSCS+ , HCS2 - , and c-HSCS are reported for the first time. The IR absorption lines of the t-HSCS radical, t-HC(S)SH, and c-HC(S)SH were also identified; their wavenumbers are similar to those reported for these species in an Ar matrix. The corresponding spectra of the13 C,34 S, and D isotopic variants of these species were observed. The assignments were made according to the expected chemical behavior, predicted potential energies of associated reactions, and a comparison of observed and predicted wavenumbers and their13 C,34 S, and D isotopic ratios. In contrast to the observed significant red shifts of the OH-stretching wavenumbers of HOCO+ and HOCS+ in solid p-H2 compared to those in the gaseous phase due to proton sharing with H2 , the wavenumber of the HS-stretching mode of HSCS+ in solid p-H2 (2477.2 cm-1 ) is similar to the anharmonic wavenumber of HSCS+ (2424 cm-1 ) predicted with the B3LYP/aug-cc-pVTZ method, indicating that the sharing of a proton between HSCS+ and neighboring H2 molecules is insignificant.

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