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

Masashi Tsuge*, Yuan-Pern Lee

*Corresponding author for this work

Research output: Contribution to journalArticle

1 Scopus citations

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-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-13) 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-14) 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 13C, 34S, 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 13C, 34S, 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.

Original languageEnglish
Pages (from-to)9641-9653
Number of pages13
JournalPhysical Chemistry Chemical Physics
Volume19
Issue number14
DOIs
StatePublished - 1 Jan 2017

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