화학공학소재연구정보센터
Journal of Chemical Physics, Vol.112, No.4, 1823-1834, 2000
Laser spectroscopy of jet-cooled ethyl radical: Infrared studies in the CH2 stretch manifold
A glow discharge, slit supersonic expansion in conjunction with direct infrared laser absorption methods has been utilized to record high resolution vibration-rotation spectra of the CH3-CH2 ethyl radical. The slit supersonic expansion results in efficient rotational cooling from discharge temperatures down to T-rot approximate to 14 K, permitting unambiguous rotational assignment and spectral analysis for the first time. Furthermore, a discharge on/discharge off data collection scheme permits clean discrimination between spectral contributions from radical vs precursor absorption. Spectra for both symmetric and asymmetric CH2 stretch manifolds are observed. Least-squares fits of transition frequencies out of the K = 0 ground state manifold to a near prolate top model Hamiltonian reproduce the data to within the 7 MHz experimental uncertainty and provides rotational constants for both ground and vibrationally excited symmetric/asymmetric CH2 stretch states. The band origins for the CH2 stretch vibrations [3037.018 96(12) cm(-1) and 3128.693 69(13) cm(-1)] are in reasonable agreement with ab initio theory; though predictions for relative intensities of the two bands are off by nearly an order of magnitude and indicate that the transition moment vector is tilted 33 degrees away from each C-H bond toward the C-C bond axis. Structural analysis based on the measured B and C rotational constants imply a C-C bond distance of 1.49 Angstrom. This is consistent with partial (approximate to 15%) double bond character for the ethyl radical carbon frame and in excellent agreement with theoretical predictions.