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 simplified emission spectra and the associated x-ray absorption spectra are modeled using straightforward procedures and compared with semiempirical ground-state molecular-orbital calculations. Good agreement is observed between the present experimental and theoretical results for valence-orbital energies and those obtained from ultraviolet photoemission, and between relative radiative yields determined both experimentally and theoretically in this work.
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Copyright American Physical Society, used with permission
Perera, R. C.,
Cowan, P. L.,
Lindle, D. W.,
LaVilla, R. E.,
Deslattes, R. D.
Molecular-orbital Studies Via Satellite-free X-ray Fluorescence: Cl-K Absorption and K–Valence-level Emission Spectra of Chlorofluoromethanes.
Physical Review A, 43(7),
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