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Title: Analysis of X-ray adsorption edges: L2,3 edge of FeCl4

Abstract

We describe a detailed analysis of the features of the X-ray adsorption spectra at the Fe L2,3 edge of FeCl4. The objective of this analysis is to explain the origin of the complex features in relation to properties of the wavefunctions, especially for the excited states. These properties include spin-orbit and ligand field splittings where a novel aspect of the dipole selection rules is applied to understand the influence of these splittings on the spectra. We also explicitly take account of the intermediate coupling of the open core and valence shell electrons. Our analysis also includes comparison of theory and experiment for the Fe L2,3 edge and comparison of theoretical predictions for the Fe3+ cation and FeCl4-. Here, the electronic structure is obtained from theoretical wavefunctions for the ground and excited states.

Authors:
ORCiD logo [1];  [2];  [3]; ORCiD logo [3];  [3]
  1. Univ. of North Texas, Denton, TX (United States)
  2. Consultant, Austin, TX (United States)
  3. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1422309
Alternate Identifier(s):
OSTI ID: 1413019
Report Number(s):
PNNL-SA-131505
Journal ID: ISSN 0021-9606; 48274; KC0302060
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 147; Journal Issue: 22; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Environmental Molecular Sciences Laboratory; Relativistic effects; Spin-orbit interactions; Field theory; Dirac-Coulomb Hamiltonian; Ligand fields; Gaussian broadening; Angular momentum coupling; Selection rule; Differential geometry; Excitation energies

Citation Formats

Bagus, Paul S., Nelin, Connie J., Ilton, Eugene S., Sassi, Michel J., and Rosso, Kevin M. Analysis of X-ray adsorption edges: L2,3 edge of FeCl4–. United States: N. p., 2017. Web. doi:10.1063/1.5006223.
Bagus, Paul S., Nelin, Connie J., Ilton, Eugene S., Sassi, Michel J., & Rosso, Kevin M. Analysis of X-ray adsorption edges: L2,3 edge of FeCl4–. United States. doi:10.1063/1.5006223.
Bagus, Paul S., Nelin, Connie J., Ilton, Eugene S., Sassi, Michel J., and Rosso, Kevin M. Tue . "Analysis of X-ray adsorption edges: L2,3 edge of FeCl4–". United States. doi:10.1063/1.5006223. https://www.osti.gov/servlets/purl/1422309.
@article{osti_1422309,
title = {Analysis of X-ray adsorption edges: L2,3 edge of FeCl4–},
author = {Bagus, Paul S. and Nelin, Connie J. and Ilton, Eugene S. and Sassi, Michel J. and Rosso, Kevin M.},
abstractNote = {We describe a detailed analysis of the features of the X-ray adsorption spectra at the Fe L2,3 edge of FeCl4. The objective of this analysis is to explain the origin of the complex features in relation to properties of the wavefunctions, especially for the excited states. These properties include spin-orbit and ligand field splittings where a novel aspect of the dipole selection rules is applied to understand the influence of these splittings on the spectra. We also explicitly take account of the intermediate coupling of the open core and valence shell electrons. Our analysis also includes comparison of theory and experiment for the Fe L2,3 edge and comparison of theoretical predictions for the Fe3+ cation and FeCl4-. Here, the electronic structure is obtained from theoretical wavefunctions for the ground and excited states.},
doi = {10.1063/1.5006223},
journal = {Journal of Chemical Physics},
number = 22,
volume = 147,
place = {United States},
year = {2017},
month = {12}
}

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