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• W2028546821 abstract "A study was made of the influence of the chalcogen X on the magnetic and electrical properties of Pu2O2X (X = O, S, Se) compounds and on bonding in these hexagonal compounds, isostructural with the corresponding rare-earth compounds. The comparison of the cell volumes of Nd2O2X and Pu2O2X compounds showed that the Pu3+ crystal radius decreased from β-Pu2O3 to Pu2O2Se as “5f delocalization” and 5f-p overlap increased. These plutonium compounds were all found to be antiferromagnetic. This was caused by superexchange coupling interactions via p orbitals of the oxygen and chalcogen ions. The Néel temperature increased from β-Pu2O3 (26 K) to Pu2O2S (28 K) then to Pu2O2Se (34 K) showing that 5f-p covalency was enhanced as the chalcogen electronegativity decreased and the p radial extent increased. The hexagonal β-Pu2O3 was found to be an insulator while both other compounds were semiconductors with gaps around 0.5 eV. These gaps were interpreted as the energy separation between the 6d-7s conduction band and the np band of the chalcogen X with some overlap of the occupied 5f states and the np band. A simple electron band scheme of these compounds is proposed on such assumptions. Nous avons étudié l'influence de l'élément chalcogène X sur les propriétés magnétiques et électriques des oxychalcogénures Pu2O2X (X = O, S, Se) ainsi que sur la liaison chimique dans ces composés hexagonaux, isostructuraux des composés similaires de terres rares. En comparant les volumes de maille de Pu2O2X et de Nd2O2X, on montre que le rayon cristallin de Pu décroit de Pu2O3à Pu2O2Se avec l'augmentation des recouvrements 5f-p et de la “délocalisation” des électrons 5f. Ces composés sont tous antiferromagnétiques, la température de Néel augmentant de Pu2O3 (26 K) à Pu2O2Se (34 K). Cela montre que, lorsque l'électronégativité de X diminue, les interactions de superéchange à travers O2− et X2− se renforcent ainsi que la covalence 5f-p. Pu2O3 hexagonal est isolant alors que les deux autres composés sont semiconducteurs avec un gap voisin de 0,5 eV. Nous avons considéré ce gap comme la différence d'énergie entre la bande de conduction 7s-6d et la bande np du chalcogène X. Les états 5f occupés sont situés juste au-dessous de la bande np en la recouvrant partiellement. A partir de ces hypothèses nous avons proposé un modèle de bandes simple pour ces composés." @default.
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• W2028546821 date "1983-04-01" @default.
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• W2028546821 title "Crystal chemistry, magnetic, and electrical properties of hexagonal plutonium oxide chalcogenides: Pu2O2X, X = O, S, Se" @default.
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• W2028546821 doi "https://doi.org/10.1016/0022-4596(83)90009-9" @default.
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