ID 111232
Title Alternative
Apparent Chemical Shifts at X-ray Absorption Edges of 3d-, 4f-, 5d- and 5p-elements for Empirical Chemical State Analysis
Author
Yukumoto, Akira The University of Tokushima
Keywords
XANES
apparent chemical shift
lanthanoid
3d transition elements
period 6 elements
Content Type
Journal Article
Description
様々な3d遷移元素V,Cr,Mn,Co,Ni,Cu化合物のK吸収端,希土類元素Ce,Pr,Eu,Tb化合物及び5d,5pブロック元素Pt,Pb,Bi化合物のL1,3吸収端X線吸収スペクトルを測定し,見かけ上の化学シフトについて包括的な検討を行った.酸化数に対する見かけ上の吸収端エネルギーに関する元素間,吸収端ごとのシフト量及びその線形性に関する傾向を評価するとともに,XANESの化学シフトを半経験的な価数評価に利用する際の留意点について言及した.希土類元素ではいずれもL1吸収端のシフトがL3吸収端のものより大きく,二価三価の酸化数を取り得る元素のシフト値は三価四価を取り得る元素より大きかった.3d遷移金属及び5d,5pブロック元素では同一グループ内でシフト量に大きなばらつきはみられなかった.
Description Alternative
X-ray absorption spectra of 3d transition elements at K-edge, lanthanoides and the other period 6 elements at L-edges for 105 compounds were recorded by a laboratory-type X-ray absorption spectrometer to elucidate the chemical shift comprehensively for empirical oxidation state analysis. Apparent absorption edge energies were determined at a half of the normalized XANES, and each the chemical shifts were estimated by a slope of the edge energy plotted as a function of the oxidation number. Evaluated apparent chemical shifts, linearity of the valence dependency, and the deviations were discussed based on chemical element groups, each element being within the group, and absorption edges. The apparent chemical shifts for K-edge of 3d transition elements lay within 2±0.5 eV/valences except for Cu. The chemical shifts for L-edges of lanthanoid compounds were about 2-4 times larger than those for K-edges of 3d transition elements, and shifts for Pt, Pb and Bi of the same period elements at L-edges were at most 1.3 eV/valences. Chemical shifts for lanthanoid elements at L1-edge were 1.5 times larger than those for corresponding L3-edges.
Journal Title
BUNSEKI KAGAKU
ISSN
05251931
NCID
AN00222633
AA11681958
Publisher
日本分析化学会
Volume
62
Issue
6
Start Page
555
End Page
563
Published Date
2013-06-27
Rights
© The Japan Society for Analytical Chemistry 2013
EDB ID
DOI (Published Version)
URL ( Publisher's Version )
FullText File
language
jpn
TextVersion
Publisher
departments
Science and Technology