Molecular-orbital Studies Via Satellite-free X-ray Fluorescence: Cl-K Absorption and K–Valence-level Emission Spectra of Chlorofluoromethanes

Authors

Rupert C. Perera, Lawrence Berkeley National LaboratoryFollow
P. L. Cowan, Argonne National Laboratory
Dennis W. Lindle, University of Nevada, Las VegasFollow
R. E. LaVilla, National Institute ofStandards and Technology,
T. Jach, National Institute ofStandards and Technology,
R. D. Deslattes, National Institute ofStandards and Technology,

Document Type

Article

Publication Date

4-1991

Publication Title

Physical Review A

Volume

43

Issue

7

First page number:

3609

Last page number:

3618

Abstract

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.

Keywords

Atomic orbitals; Chlorofluoromethane; Emission spectroscopy; Ionization; Molecular orbitals; Photoemission

Disciplines

Analytical Chemistry | Atomic, Molecular and Optical Physics | Biological and Chemical Physics | Elementary Particles and Fields and String Theory | Physical Chemistry

Language

English

Permissions

Copyright American Physical Society, used with permission

Repository Citation

Perera, R. C., Cowan, P. L., Lindle, D. W., LaVilla, R. E., Jach, T., Deslattes, R. D. (1991). 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), 3609-3618.
https://digitalscholarship.unlv.edu/chem_fac_articles/74