TY - JOUR
T1 - Diminished cage effect in solid p-H2
T2 - Infrared spectra of ClSCS, ClCS, and ClSC in an irradiated p-H2 matrix containing Cl 2 and CS2
AU - Huang, Chiung Wei
AU - Lee, Yaw Chang
AU - Lee, Yuan-Pern
PY - 2010/4/28
Y1 - 2010/4/28
N2 - Irradiation of a p H2 matrix containing Cl2 and CS2 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 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 13C - and 34S -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 H2 is diminished so that isolated Cl was produced via photodissociation of Cl2 in situ and subsequently reacted with CS2 to form ClSCS, but not ClC (S) SCl, upon annealing; typically ClC (S) SCl was produced as the major product on irradiation of noble-gas matrices containing Cl2 and CS2. Observation of ClSCS but not ClCS2 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 CS2 were produced; subsequent annealing of the irradiated matrix produced ClSC and ClCS via barrierless paths.
AB - Irradiation of a p H2 matrix containing Cl2 and CS2 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 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 13C - and 34S -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 H2 is diminished so that isolated Cl was produced via photodissociation of Cl2 in situ and subsequently reacted with CS2 to form ClSCS, but not ClC (S) SCl, upon annealing; typically ClC (S) SCl was produced as the major product on irradiation of noble-gas matrices containing Cl2 and CS2. Observation of ClSCS but not ClCS2 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 CS2 were produced; subsequent annealing of the irradiated matrix produced ClSC and ClCS via barrierless paths.
UR - http://www.scopus.com/inward/record.url?scp=77952418639&partnerID=8YFLogxK
U2 - 10.1063/1.3386578
DO - 10.1063/1.3386578
M3 - Article
C2 - 20441271
AN - SCOPUS:77952418639
SN - 0021-9606
VL - 132
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 16
M1 - 164303
ER -