Journal of Chemical Physics, Vol.109, No.18, 7793-7802, 1998
High-resolution infrared spectroscopy of jet-cooled allyl radical (CH2-CH-CH2) : In-phase (nu(1)) and out-of-phase (nu(13)) antisymmetric CH2 stretching vibrations
High-resolution infrared spectra of jet-cooled allyl (CH2-CH-CH2) radical in the CH2 stretching region are obtained in a slit jet discharge spectrometer. Over 200 transitions are observed in the 3100-3140 cm(-1) region, which have been rigorously assigned to "in-phase" (v(1)) and "out-of-phase" (v(13)) coupling of antisymmetric CH stretch excitations on each of the equivalent CH2 subunits. Origins for the two bands are determined to be 3113.98 488(89) cm(-1) (v(1)) and 3110.59 857(36) cm(-1) (v(13)), respectively. The data are reasonably well fit to semirigid asymmetric rotor behavior for the K-a less than or equal to 2 levels populated in the slit jet at T-rot approximate to 20 K, though not to within the experimental precision, which provides some indication of perturbations in the upper states. The sign and magnitude of the +3.4 cm(-1) splitting between ''in-phase'' and ''out-of-phase'' excitations are in good qualitative agreement with a simple electrostatic model of dipole-dipole coupling between the two ''local mode'' CH2 groups. Due to sub-Doppler resolution (Delta v approximate to 70 MHz) in the slit jet expansion, quantum-state-dependent excess broadening of the rovibrational transitions is observed, which can be ascribed to spin-rotation interactions. Based on a least squares analysis of the high-resolution line shapes, the data are consistent with a spin rotation constant of epsilon(aa) approximate to -67(25) MHz.
Keywords:RESONANT MULTIPHOTON IONIZATION, FLASH KINETIC SPECTROSCOPY;DIODE-LASER SPECTROSCOPY, ABSORPTION-SPECTROSCOPY, SUPERSONICJET, SINGLET METHYLENE, MOLECULAR-IONS, OH RADICALS, SPECTRUM;EXPANSION