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The optical absorption of Cr(3+)-doped fluoride glasses has been investigated. The lowest energy absorption band (4)A2 → (4)T2 shows distinct interference dips due to spin-orbit coupling between (4)T2, (2)E and (2)T1 excited states. The dips were analyzed using an analytical method proposed by Bussière et al. ( J. Phys. Chem. A 2003 , 107 , 1258 ) based on coupled potential energy surfaces. Then a theoretical crystal-field analysis based on the Racah tensor algebraic method was carried on Cr(3+) ions occupying octahedral site symmetry in the fluoride glasses. Satisfactory correlations were obtained between the experimental and calculated energy levels. The fitting of the interference dips also provided a measure of the spin-orbit coupling constant for Cr(3+) in fluoride glasses, intermediate between the theoretical value calculated for a fluoride crystal and the value deduced from Racah parameters.