Infrared absorption of gaseous ClCS detected with time-resolved Fourier-transform spectroscopy.
A transient infrared absorption spectrum of gaseous ClCS was detected with a step-scan Fourier-transform spectrometer coupled with a multipass absorption cell. ClCS was produced upon irradiating a flowing mixture of Cl2CS and N2 or CO2 with a KrF excimer laser at 248 nm. A transient band in the region of 1160-1220 cm-1, which diminished on prolonged reaction, is assigned to the C-S stretching (nu1) mode of ClCS. Calculations with density-functional theory (B3P86 and B3LYP/aug-cc-pVTZ) predict the geometry, vibrational wave numbers, and rotational parameters of ClCS. The rotational contour of the spectrum of ClCS simulated based on predicted rotational parameters agrees satisfactorily with experimental observation; from spectral simulation, the band origin is determined to be at 1194.4 cm-1. Reaction kinetics involving ClCS, CS, and CS2 are discussed.
Transient infrared spectra of CH3SOO and CH3SO observed with a step-scan Fourier-transform spectrometer.
A step-scan Fourier-transform spectrometer coupled with a multipass absorption cell was employed to monitor time-resolved infrared absorption of transient species produced upon irradiation at 248 nm of a flowing mixture of CH(3)SSCH(3) and O(2) at 260 K. Two transient bands observed with origins at 1397±1 and 1110±3 cm(-1) are tentatively assigned to the antisymmetric CH(3)-deformation and O-O stretching modes of syn-CH(3)SOO, respectively; the observed band contour indicates that the less stable anti-CH(3)SOO conformer likely contributes to these absorption bands. A band with an origin at 1071±1 cm(-1), observed at a slightly later period, is assigned to the S=O stretching mode of CH(3)SO, likely produced via secondary reactions of CH(3)SOO. These bands fit satisfactorily with vibrational wavenumbers and rotational contours simulated based on rotational parameters of syn-CH(3)SOO, anti-CH(3)SOO, and CH(3)SO predicted with density-functional theories B3LYP/aug-cc-pVTZ and B3P86/aug-cc-pVTZ. Two additional bands near 1170 and 1120 cm(-1) observed at a later period are tentatively assigned to CH(3)S(O)OSCH(3) and CH(3)S(O)S(O)CH(3), respectively; both species are likely produced from self-reaction of CH(3)SOO. The production of SO(2) via secondary reactions was also observed and possible reaction mechanism is discussed.
Fragment Rotational State Distributions From The Dissociation Of NeIBr: Experimental And Theoretical Results
The IBr fragment rotational state distributions that result when the NeIBr van der Waals molecule undergoes vibrational predissociation have been measured in a pump–probe laser‐induced fluorescence experiment. Independent of initial vibrational state and the number of quanta of vibrational energy lost from the I–Br coordinate, the rotational distributions extend over the full range of energetically accessible states. From the observation of energetic constraints on the rotational distribution, the dissociation energy (D0) is calculated to be 65.5±1.2 cm−1 for the A electronic state, v=16. For the X electronic state, v=0, D0=71.8±1.2 cm−1. Quantum mechanical bound state calculations carried out on a model A electronic state potential energy surface are in quantitative agreement with this result. The rotational distributions are broader than that predicted by either a Franck–Condon or classical impulsive model for the dissociation. The distributions are qualitatively in accord with classical trajectory calc...