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Calculation of the electronic structure of AmO 2 and Pr 6 O 11 for XANES analysis with redox property
Author(s) -
Suzuki Chikashi,
Nishi Tsuyoshi,
Nakada Masami,
Akabori Mitsuo,
Hirata Masaru,
Kaji Yoshiyuki
Publication year - 2009
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.22191
Subject(s) - xanes , actinide , electronic structure , chemistry , spectral line , oxide , metal , atomic physics , crystallography , physics , computational chemistry , inorganic chemistry , organic chemistry , astronomy
Abstract We calculated X‐ray absorption near‐edge structure (XANES) of Am L III of AmO 2 and Pr L III of Pr 6 O 11 using the relativistic discrete‐variational (DV)‐Xα method based on the Dirac–Slater method, and compared it with the experimental spectra. These spectra were calculated on a model of AmO 2 ([AmO 8 ] 12− ) and Pr 6 O 11 ([PrO 8 ] 12− ). In spite of using small cluster models, the calculated spectra were in good agreement with the experiment ones. Besides, we calculated the electronic structure of AmO 2 and Pr 6 O 11 to analyze the peak structures of XANES. From this calculation, it was found that O s, p, and f components had influence on the specific peak structures but that O d component had influence on various peak structures for AmO 2 and Pr 6 O 11 . From this result, it was suggested that the change of the electronic structure of actinide 6d and O d or f was important for actinide L III XANES corresponding to oxygen to metal ratio in the oxide nuclear fuel. On the basis of these results, we calculated the fine structures of densities of states and the transition energy from the HOMO to the white line of AmO 2 , UO 2 , and Pr 6 O 11 and investigated redox properties of Am and U in the oxide nuclear fuel with the evaluation of validity of Pr as simulant materials of Am. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2009