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- W1996032406 abstract "Vibrationally excited H2O, HOD, and D2O molecules formed by unimolecular elimination from deutero-substituted ethanol molecules C2H5OH*, C2H5OD*, CH2DCH2OH*, and CH2DCH2OD* with an excitation energy of about 100 kcal mol−1 were observed by infrared chemiluminescence in the 2400–3900 cm−1 range. The activated ethanol molecules were produced via the successive reactions H+CH2ICH2OH→HI+CH2CH2OH and H+CH2CH2OH→CH3CH2OH* in a fast flow reactor that was observed with a Fourier transform spectrometer. The vibrational distributions of the H2O, HOD, and D2O molecules were determined by computer simulation of the experimental spectra; the distributions decline with increasing vibrational energy giving 〈fv〉=0.15 and 〈fv〉=0.14 for H2O and HOD from the decomposition of C2H5OH* and C2H5OD*, respectively. The vibrational energy in the bending mode of H2O is comparable to the energy in the stretching modes. Comparison with the statistical vibrational distributions shows a substantial overpopulation of the bending levels and a preferential excitation of one O–H or O–D stretching quantum in HOD from C2H5OD or CH2DCH2OH, respectively, i.e., in the newly formed bond. Kinetic isotope effects of [H2O]/[HOD]=3.6±0.8 and [HOD]/[D2O]=3.1±0.8 were found for the two elimination pathways of CH2DCH2OH* and CH2DCH2OD*, respectively, which agree with calculated RRKM values of kH2O/kHOD=3.2 and kHOD/kD2O=2.7." @default.
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- W1996032406 date "1996-11-08" @default.
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- W1996032406 title "Unimolecular decomposition of chemically activated deutero‐substituted ethanol molecules studied by infrared chemiluminescence from H<sub>2</sub>O, HOD, and D<sub>2</sub>O" @default.
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- W1996032406 doi "https://doi.org/10.1063/1.472716" @default.
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