skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: An Independent Confirmation of the Correlation of Uf4 Primary Peaks and Satellite Structures of U VI, U V and U IV in Mixed Valence Uranium Oxides by Two-Dimensional Correlation Spectroscopy

Abstract

Two-Dimensional (2D) Correlation Spectroscopy was used to resolve the positions and correlations among U4f primary peaks and satellite structures that evolved as U VI was progressively reduced by a constant high flux of monochromatic Al Kα X-rays during X-ray photoelectron spectroscopy (XPS). Synchronous and asynchronous 2D maps of these results are consistent with previous assignments to U IV, U V and U VI components of the solid. The synchronous spectra confirmed the negative correlation between U VI and U IV components. The asynchronous spectra displayed cross-peaks that were characteristic of peak shift and confirmed the role of U V as a reactive intermediate in the reduction reaction of U VI to U IV. Simulations of 2D correlation maps using synthetic spectra of the primary peaks showed that the presence of highly overlapped peaks centered within 2 eV cannot be distinguished without the presence of additional cross-peaks. The maps have therefore confirmed the existence of three dominant oxidation states, and identified positions of U IV, U V, and U VI U4f primary peaks and satellite structures that are consistent with previous peak-fitting efforts. Satellite structures also showed out-of-phase correlations among the different oxidation states, confirming previous assignments.

Authors:
 [1];  [2]
  1. Umea Univ. (Sweden)\
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
949913
Report Number(s):
PNNL-SA-60685
Journal ID: ISSN 0039-6028; SUSCAS; KC0303020; TRN: US0901900
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Surface Science
Additional Journal Information:
Journal Volume: 602; Journal Issue: 24; Journal ID: ISSN 0039-6028
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; URANIUM OXIDES; VALENCE; X-RAY PHOTOELECTRON SPECTROSCOPY; PATTERN RECOGNITION; XPS; uranium; two-dimension correlation spectroscopy; chemometrics

Citation Formats

Boily, Jean F., and Ilton, Eugene S. An Independent Confirmation of the Correlation of Uf4 Primary Peaks and Satellite Structures of UVI, UV and UIV in Mixed Valence Uranium Oxides by Two-Dimensional Correlation Spectroscopy. United States: N. p., 2008. Web. doi:10.1016/j.susc.2008.09.015.
Boily, Jean F., & Ilton, Eugene S. An Independent Confirmation of the Correlation of Uf4 Primary Peaks and Satellite Structures of UVI, UV and UIV in Mixed Valence Uranium Oxides by Two-Dimensional Correlation Spectroscopy. United States. doi:10.1016/j.susc.2008.09.015.
Boily, Jean F., and Ilton, Eugene S. Fri . "An Independent Confirmation of the Correlation of Uf4 Primary Peaks and Satellite Structures of UVI, UV and UIV in Mixed Valence Uranium Oxides by Two-Dimensional Correlation Spectroscopy". United States. doi:10.1016/j.susc.2008.09.015.
@article{osti_949913,
title = {An Independent Confirmation of the Correlation of Uf4 Primary Peaks and Satellite Structures of UVI, UV and UIV in Mixed Valence Uranium Oxides by Two-Dimensional Correlation Spectroscopy},
author = {Boily, Jean F. and Ilton, Eugene S.},
abstractNote = {Two-Dimensional (2D) Correlation Spectroscopy was used to resolve the positions and correlations among U4f primary peaks and satellite structures that evolved as UVI was progressively reduced by a constant high flux of monochromatic Al Kα X-rays during X-ray photoelectron spectroscopy (XPS). Synchronous and asynchronous 2D maps of these results are consistent with previous assignments to UIV, UV and UVI components of the solid. The synchronous spectra confirmed the negative correlation between UVI and UIV components. The asynchronous spectra displayed cross-peaks that were characteristic of peak shift and confirmed the role of UV as a reactive intermediate in the reduction reaction of UVI to UIV. Simulations of 2D correlation maps using synthetic spectra of the primary peaks showed that the presence of highly overlapped peaks centered within 2 eV cannot be distinguished without the presence of additional cross-peaks. The maps have therefore confirmed the existence of three dominant oxidation states, and identified positions of UIV, UV, and UVI U4f primary peaks and satellite structures that are consistent with previous peak-fitting efforts. Satellite structures also showed out-of-phase correlations among the different oxidation states, confirming previous assignments.},
doi = {10.1016/j.susc.2008.09.015},
journal = {Surface Science},
issn = {0039-6028},
number = 24,
volume = 602,
place = {United States},
year = {2008},
month = {9}
}