When Ce 3+ ions substitute for La 3+ in a LaCl 3 host, the lowest-energy peak in

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When Ce3+ ions substitute for La3+ in a LaCl3 host, the lowest-energy peak in the photoluminescence excitation spectrum falls at 281 nm, whereas a similar substitution in the double-perovskite host Cs2NaLaCl6 shifts the lowest-energy peak in the excitation spectrum to 342 nm. The La3+ ion in LaCl3 sits in a nine-coordinate tricapped trigonal-prismatic site, while in Cs2NaLaCl6 the La3+ ion is octahedrally coordinated.

(a) Would you predict a larger, smaller, or similar centroid shift in Cs2NaLaCl6?

(b) How will differences in the coordination environment shift the lowest-energy Ce3+ excitation peak in Cs2NaLaCl6?

(c) Is the observed shift in the Ce3+ excitation spectrum due to the centroid shift, the change in coordination, or both?

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Solid State Materials Chemistry

ISBN: 9780521873253

1st Edition

Authors: Patrick M. Woodward, Pavel Karen, John S. O. Evans, Thomas Vogt

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