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Local Ir dedimerization followed by ligand-hole hopping in X-ray irradiated thiospinel

X線照射されたチオスピネルにおけるリガンドホールホッピングがもたらすイリジウムダイマーの消失

平賀 晴弘*; 松村 大樹; 堀金 和正*; 水木 純一郎*

Hiraka, Haruhiro*; Matsumura, Daiju; Horigane, Kazumasa*; Mizuki, Junichiro*

The extended X-ray-absorption fine structure of a spinel CuIr$$_{2}$$(S$$_{0.95}$$Se$$_{0.05}$$)$$_{4}$$ powder sample, which has the charge-ordered temperature $$T_{rm{CO}}$$ = 190 K, was determined at the Ir $$L_{3}$$ edge for a wide temperature range. All the local structure parameters on the Ir-Ir bonds signified the second structural change at $$T^{*} sim$$ 70 K. Remarkably, the number of Ir dimers decreased by $$sim$$ 10% below $$T^{*}$$, which indicates partial dedimerization by X-ray irradiation. We also reanalyzed the resistance data of CuIr$$_{2}$$S$$_{4}$$ with the variable-range hopping model by focusing on the density of states. The X-ray-induced decrease in resistance was quantitatively explained as a result of the increase in the density of states, which was attributed to the release of holes from the 10%-dedimerized Ir ions. We suppose that the released holes hop over the ligand chalcogen site.

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パーセンタイル:100

分野:Chemistry, Multidisciplinary

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