期刊
JOURNAL OF SOLID STATE CHEMISTRY
卷 178, 期 2, 页码 464-469出版社
ACADEMIC PRESS INC ELSEVIER SCIENCE
DOI: 10.1016/j.jssc.2004.09.020
关键词
lanthanide complexes; Ce3+; halides; elpasolites.; bond lengths; excited states; f to d transitions ab initio calculations; solvent effects
Ligand and solvent effects on the bond length shift experienced by complexes of lanthanide ions upon 4f -> 5d excitation, addressed by means of ab initio embedded cluster calculations, are presented on the clusters (CeF6)(3-), (CeCl6)(3-), and (CeBr6)(3-) in solid elpasolites, in liquid acetonitrile and in vacuo. Previous predictions of bond length shortening upon 4f -> 5d((t2g)) excitation seem to be general and, in particular, chloride and bromide compounds in liquid solution are predicted to be good candidates for excited-state EXAFS measurements of the distortion signs. A quantitative analysis of contributions to the bond length shifts is presented, which shows the importance of ligand field effects and points out insufficiencies in the Judd-Morrison model proposed to account for 4f -> 5d transitions in crystals. (c) 2004 Elsevier Inc. All rights reserved.
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