Molecular-orbital studies via satellite-free x-ray fluorescence: Cl K absorption and K --valence-level emission spectra of chlorofluoromethanes

Journal Article · Mon Apr 01 00:00:00 EST 1991 · Physical Review, A; (USA)

DOI:https://doi.org/10.1103/PhysRevA.43.3609· OSTI ID:5610262

Perera, R C.C. ^[1]; Cowan, P L; Lindle, D W; LaVilla, R E; Jach, T; Deslattes, R D ^[2]

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1. Advanced Light Source, Lawrence Berkeley Laboratory, Berkeley, California 94720 (US)
2. Quantum Metrology Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899 (US)

X-ray absorption and emission measurements in the vicinity of the chlorine {ital 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 1{ital s} 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 {ital 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 1{ital s} 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.

• DOE Contract Number: AC03-76SF00098
• OSTI ID: 5610262
• Journal Information: Physical Review, A; (USA), Vol. 43:7; ISSN 1050-2947
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
CHLORINATED ALIPHATIC HYDROCARBONS
X-RAY SPECTRA
FLUORINATED ALIPHATIC HYDROCARBONS
ABSORPTION SPECTRA
ELECTRONIC STRUCTURE
EMISSION SPECTRA
K SHELL
MOLECULAR ORBITAL METHOD
SYNCHROTRON RADIATION
VALENCE
BREMSSTRAHLUNG
ELECTROMAGNETIC RADIATION
HALOGENATED ALIPHATIC HYDROCARBONS
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
RADIATIONS
SPECTRA
640302* - Atomic
Molecular & Chemical Physics- Atomic & Molecular Properties & Theory