標題: Diminished cage effect in solid p-H(2): Infrared spectra of CISCS, CICS, and CISC in an irradiated p-H(2) matrix containing Cl(2) and CS(2)
作者: Huang, Chiung-Wei
Lee, Yaw-Chang
Lee, Yuan-Pern
應用化學系
應用化學系分子科學碩博班
Department of Applied Chemistry
Institute of Molecular science
公開日期: 28-Apr-2010
摘要: Irradiation of a p-H(2) matrix containing Cl(2) and CS(2) at 3.3 K with laser emission at 340 nm followed by annealing of the matrix produced main features at 1479.5 and 1480.8 cm(-1). These lines are attributed to v(1) (SCS antisymmetric stretching) mode of ClSCS. Irradiation of the matrix at 355 nm decomposes ClSCS. Products CS (1272.2 and 1271.1 cm(-1)), ClCS (1193.9/1191.9 and 637.5 cm(-1)), and ClSC (1137.0 cm(-1)) were observed upon annealing. The assignments were based on comparison of observed vibrational wavenumbers and (13)C- and (34)S-isotopic ratios with those predicted with density-functional theories (B3LYP and BPW91/aug-cc-pVTZ). These results demonstrate that the cage effect of solid p-H(2) is diminished so that isolated Cl was produced via photodissociation of Cl(2) in situ and subsequently reacted with CS(2) to form ClSCS, but not ClC(=vS)SCl, upon annealing; typically ClC(vS)SCl was produced as the major product on irradiation of noble-gas matrices containing Cl(2) and CS(2). Observation of ClSCS but not ClCS(2) is consistent with the theoretical prediction that only formation of the former proceeds via a barrierless path. Similarly, upon irradiation of ClSCS at 355 nm, Cl, CS, and CS(2) were produced; subsequent annealing of the irradiated matrix produced ClSC and ClCS via barrierless paths. c 2010 American Institute of Physics. [doi: 10.1063/1.3386578]
URI: http://dx.doi.org/10.1063/1.3386578
http://hdl.handle.net/11536/5503
ISSN: 0021-9606
DOI: 10.1063/1.3386578
期刊: JOURNAL OF CHEMICAL PHYSICS
Volume: 132
Issue: 16
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