Infrared spectra of HSCS+, c-HSCS, and HCS2- produced on electron bombardment of CS2 in solid para-hydrogen

Abstract

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-H-2) 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 (v(1)), 1525.6 (v(2)), and 919.6 cm(-1) (v(3)) decreased through neutralization of HSCS+ with trapped electrons. During this period, the intensities of the lines of HCS2- at 2875.7 (v(1)), 1249.9 (v(5)), 1003.2 (v(6)), and 814.3 cm (1) (v(4)) 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 the C-13, S-34, 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 their C-13, S-34, and D isotopic ratios. In contrast to the observed significant red shifts of the OH-stretching wavenumbers of HOCO+ and HOCS+ in solid p-H-2 compared to those in the gaseous phase due to proton sharing with H-2, the wavenumber of the HS-stretching mode of HSCS+ in solid p-H-2 (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 H-2 molecules is insignificant.