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Material and Spectroscopic Properties of Cr in Different Oxidation States in Calcium Fluorapatite

Published online by Cambridge University Press:  15 February 2011

J. B. Gruber
Affiliation:
Department of Physics, San Jose State University, San Jose, CA 95192
J. A. Hutchinson
Affiliation:
Night Vision and Electronic Sensors Directorate, Fort Belvoir, VA 22060
D. C. Harris
Affiliation:
Chemistry Division, Research Department, NAWCWPNS, China Lake, CA 93555
M. D. Seltzer
Affiliation:
Chemistry Division, Research Department, NAWCWPNS, China Lake, CA 93555
T. H. Allik
Affiliation:
Science Applications International Corporation, McLean, VA 22102
C. A. Morrison
Affiliation:
Applied Physics Branch, U.S. Army Adelphi Lab. Center, Adelphi, MD 20783
M. P. Scripsick
Affiliation:
Department of Physics, West Virginia University, Morgantown, WV 26505
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Abstract

The material and spectroscopic properties of Cr-doped Ca5(PO4)3F (FAP) were investigated using several different chemical and physical means. From analytical titration measurements the chromium in Cr:FAP was found to be tetravalent. ESR measurements detected a trace (0.5 - 10 ppm) of Cr5+ (3d1) and no evidence for Cr3+ (3d3). The absorption and emission spectra of Cr: FAP can be interpreted on the basis of Cr4+ (3d2) ions substituting for P within a distorted tetrahedron of oxygen ions. Calculated electronic (Stark) levels for Cr4+ based on an approximate site symmetry of C4 agree well with levels deduced from an analysis of the experimental optical data. The model Hamiltonian includes Coulombic parameters B and C, interconfiguration interaction terms and the spin-orbit coupling for the 3d2 atomic configuration of Cr4+ and crystal-field terms in C4 symmetry. The parametrized Hamiltonian was diagonalized within the complete d2 configuration. Both free ion and crystal field parameters are presented.

Type
Research Article
Copyright
Copyright © Materials Research Society 1994

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