HERNANDEZ, I.; RODRIGUEZ, F.; TRESSAUD, Alain

doi:10.1021/ic800606h

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HERNANDEZ, I.
MALTA Consolider Team, Facultad de Ciencias

RODRIGUEZ, F.
MALTA Consolider Team, Facultad de Ciencias

TRESSAUD, Alain
Institut de Chimie de la Matière Condensée de Bordeaux [ICMCB]

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Inorganic Chemistry. 2008, vol. 47, n° 22, p. 10288-10298

American Chemical Society

Résumé en anglais

This work investigates the photoluminescence (PL) properties of the Cr 3+-doped and Cr3+-pure fluoroelpasolites along the A 2BMF6 series and as a function of pressure. In particular, we focus on the variation of the crystal-field spectrum and the associated PL. The results are explained on the basis of the octahedral (CrF6) 3- complex subjected either to external pressure or the internal pressure exerted by different crystal hosts. We have established structural correlations between the crystal-field parameter 10Dq and the Cr-F distance, RCr-F, from which we have determined the local structure around the Cr3+ impurity, allowing the host material effect on the Cr-F bonds to be studied. As salient features, we show, first, a weak dependence of the first excitation energy, E1, usually identified as 10Dq, with R Cr-F as E1 = KRCr-F-3.3, and, second, an increase of the Stokes shift upon RCr-F reduction or with increasing pressure. We associate this unusual behavior with the existence of state mixing among 4T2g(F), 2Eg(G), and 2T1g(G) states in the first excitation band of Cr 3+. Finally, high-pressure experiments performed on Rb 2KCrF6 indicate that the excited-state spin crossover, 2Eg(G) ↔ 4T2g(F), takes place around 7 GPa. The results indicate the suitability of the selected A 2BMF6:Cr3+ elpasolites to establish structural correlations between PL and RCr-F.< Réduire

Mots clés en anglais

Photoluminescence

Elpasolite

Crystal structure

Chromium

Inorganic compounds

Pressure

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Optical properties of the (CrF6)3- complex in A 2BMF6:Cr3+ elpasolite crystals: Variation with M-F bond distance and hydrostatic pressure

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