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The 1s x-ray absorption pre-edge structures in transition metal oxides

Abstract

We develop a general procedure to analyse the pre-edges in 1s x-ray absorption near edge structure (XANES) of transition metal oxides and coordination complexes. Transition metal coordination complexes can be described from a local model with one metal ion. The 1s 3d quadrupole transitions are calculated with the charge-transfer multiplet program. Tetrahedral coordination complexes have more intense pre-edge structures due to the local mixing of 3d and 4p states, implying a combination of 1s 3d quadrupole and 1s 4p dipole transitions. Divalent transition metal oxides can be described similar to coordination complexes, but for trivalent and tetravalent oxides, additional structures are visible in the pre-edge region due to non-local dipole transitions. The 1s 4p dipole transitions have large cross section at the 3d-band region due to the strong metal-metal interactions, which are oxygen mediated. This yields large intensity in the 3d-band region but at a different energy than the local 1s 3d quadrupole transitions because of smaller core-hole effects due to the delocalization of the excited electron.
Authors:
De Groot, Frank; [1]  Vanko, Gyoergy; [2]  Glatzel, Pieter [3] 
  1. Inorganic Chemistry and Catalysis, Utrecht University, Sorbonnelaan 16, 3584 CA Utrecht (Netherlands)
  2. KFKI Research Institute for Particle and Nuclear Physics, PO Box 49, H-1525 Budapest (Hungary)
  3. European Synchrotron Radiation Facility, BP 220, 38043 Grenoble Cedex (France)
Publication Date:
Mar 11, 2009
Product Type:
Journal Article
Resource Relation:
Journal Name: Journal of Physics. Condensed Matter; Journal Volume: 21; Journal Issue: 10; Conference: TEX2008: 1. international workshop on the theoretical calculation of ELNES and XANES, Nagoya (Japan), 2-4 Jul 2008; Other Information: PII: S0953-8984(09)94195-9; DOI: 10.1088/0953-8984/21/10/104207; Country of input: International Atomic Energy Agency (IAEA)
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; ABSORPTION; ABSORPTION SPECTROSCOPY; CROSS SECTIONS; DIPOLES; E2-TRANSITIONS; ELECTRONS; EXCITATION; HOLES; INTERACTIONS; IONS; MIXING; OXIDES; OXYGEN; QUADRUPOLES; TRANSITION ELEMENTS; X RADIATION; X-RAY SPECTROSCOPY
OSTI ID:
21263370
Country of Origin:
United Kingdom
Language:
English
Other Identifying Numbers:
Journal ID: ISSN 0953-8984; JCOMEL; TRN: GB09P0982012770
Availability:
Available from http://dx.doi.org/10.1088/0953-8984/21/10/104207;INIS
Submitting Site:
GBN
Size:
7 pages
Announcement Date:
Mar 04, 2010

Citation Formats

De Groot, Frank, Vanko, Gyoergy, and Glatzel, Pieter. The 1s x-ray absorption pre-edge structures in transition metal oxides. United Kingdom: N. p., 2009. Web. doi:10.1088/0953-8984/21/10/104207; COUNTRY OF INPUT: INTERNATIONAL ATOMIC ENERGY AGENCY (IAEA).
De Groot, Frank, Vanko, Gyoergy, & Glatzel, Pieter. The 1s x-ray absorption pre-edge structures in transition metal oxides. United Kingdom. https://doi.org/10.1088/0953-8984/21/10/104207; COUNTRY OF INPUT: INTERNATIONAL ATOMIC ENERGY AGENCY (IAEA)
De Groot, Frank, Vanko, Gyoergy, and Glatzel, Pieter. 2009. "The 1s x-ray absorption pre-edge structures in transition metal oxides." United Kingdom. https://doi.org/10.1088/0953-8984/21/10/104207; COUNTRY OF INPUT: INTERNATIONAL ATOMIC ENERGY AGENCY (IAEA).
@misc{etde_21263370,
title = {The 1s x-ray absorption pre-edge structures in transition metal oxides}
author = {De Groot, Frank, Vanko, Gyoergy, and Glatzel, Pieter}
abstractNote = {We develop a general procedure to analyse the pre-edges in 1s x-ray absorption near edge structure (XANES) of transition metal oxides and coordination complexes. Transition metal coordination complexes can be described from a local model with one metal ion. The 1s 3d quadrupole transitions are calculated with the charge-transfer multiplet program. Tetrahedral coordination complexes have more intense pre-edge structures due to the local mixing of 3d and 4p states, implying a combination of 1s 3d quadrupole and 1s 4p dipole transitions. Divalent transition metal oxides can be described similar to coordination complexes, but for trivalent and tetravalent oxides, additional structures are visible in the pre-edge region due to non-local dipole transitions. The 1s 4p dipole transitions have large cross section at the 3d-band region due to the strong metal-metal interactions, which are oxygen mediated. This yields large intensity in the 3d-band region but at a different energy than the local 1s 3d quadrupole transitions because of smaller core-hole effects due to the delocalization of the excited electron.}
doi = {10.1088/0953-8984/21/10/104207; COUNTRY OF INPUT: INTERNATIONAL ATOMIC ENERGY AGENCY (IAEA)}
journal = []
issue = {10}
volume = {21}
place = {United Kingdom}
year = {2009}
month = {Mar}
}