Infrared absorption spectra of vinyl radicals isolated in solid Ne

Abstract

Irradiation of samples of solid Ne near 3.0 K containing ethene (C(2)H(4)) with vacuum ultraviolet radiation at 120 nm from synchrotron yielded new spectral lines at 3141.0, 2953.6, 2911.5, 1357.4, 677.1, 895.3, and 857.0 cm(-1). These features are assigned to alpha-CH stretching (nu(1)), CH(2) antisymmetric stretching (nu(2)), CH(2) symmetric stretching (nu(3)), CH(2)-bending (nu(5)), HCCH cis bending (nu(7)), CH(2) out-of-plane bending (nu(8)), and alpha-CH out-of-plane bending (nu(9)) modes of C(2)H(3), respectively, based on results of (13)C- and D-isotopic experiments and quantum-chemical calculations. These calculations using density-functional theory (B3LYP and PW91PW91/aug-cc-pVTZ) predict vibrational wavenumbers, IR intensities, and isotopic ratios of vinyl radical that agree satisfactorily with our experimental results. (C) 2008 American Institute of Physics.