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Molecular-Orbital Studies Via Satellite-Free X-Ray Fluorescence: Cl-K Absorption And K–Valence-Level Emission Spectra Of Chlorofluoromethanes, Rupert C. Perera, P. L. Cowan, Dennis W. Lindle, R. E. Lavilla, T. Jach, R. D. Deslattes
Molecular-Orbital Studies Via Satellite-Free X-Ray Fluorescence: Cl-K Absorption And K–Valence-Level Emission Spectra Of Chlorofluoromethanes, Rupert C. Perera, P. L. Cowan, Dennis W. Lindle, R. E. Lavilla, T. Jach, R. D. Deslattes
Chemistry and Biochemistry Faculty Research
X-ray absorption and emission measurements in the vicinity of the chlorine K edge of the three chlorofluoromethanes have been made using monochromatic synchrotron radiation as the source of excitation. By selectively tuning the incident radiation to just above the Cl 1s single-electron ionization threshold for each molecule, less complex x-ray-emission spectra are obtained. This reduction in complexity is attributed to the elimination of multielectron transitions in the Cl K shell, which commonly produce satellite features in x-ray emission. The resulting "satellite-free" x-ray-emission spectra exhibit peaks due only to electrons in valence molecular orbitals filling a single Cl 1s vacancy. These …
Polarized X-Ray-Emission Studies Of Methyl Chloride And The Chlorofluoromethanes, Dennis W. Lindle, P. L. Cowan, T. Jach, R. E. Lavilla, R. D. Deslattes, Rupert C. Perera
Polarized X-Ray-Emission Studies Of Methyl Chloride And The Chlorofluoromethanes, Dennis W. Lindle, P. L. Cowan, T. Jach, R. E. Lavilla, R. D. Deslattes, Rupert C. Perera
Chemistry and Biochemistry Faculty Research
A new technique sensitive to molecular orientation and geometry, and based on measuring the polarization of x-ray emission, has been applied to the Cl-containing molecules methyl chloride (CH3Cl) and the chlorofluoromethanes (CF3Cl, CF2Cl2, and CFCl3) in the gas phase. Upon selective excitation using monochromatic synchrotron radiation in the Cl K-edge (Cl 1s) near-threshold region, polarization-selective x-ray emission studies reveal highly polarized molecular valence x-ray fluorescence for all four molecules. The degree and the orientation of the polarized emission are observed to be sensitive to the incident excitation energy near …