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Title: Structural and Electronic Properties of Fluoride Complexes of Nb V , Ta V , and Pa V : The Influence of Relativistic Effects on Group V Elements

Abstract

Aqueous fluorido complexes of niobium and tantalum were studied by using synchrotron‐based extended X‐ray absorption spectroscopy (EXAFS) as model systems for comparison of the structural and coordination chemistry of the group V metals Nb, Ta, and their pseudo‐homologue Pa V . The EXAFS measurements indicate differences in the coordination chemistry of Nb and Ta in these systems that were not intuitively based on their similar charge and ionic radii. The Ta speciation is dominated by six‐ and seven‐coordinate fluorido complexes, while the chemical speciation of Nb under the same conditions is dominated by its hydrolyzed oxyfluoride complexes. Quantum chemical computations were performed to more fully describe these observations, and these results are compared to our earlier study on the fluorido complexes of protactinium. Computations performed with and without the inclusion of scalar relativistic effects reveal that the differences in chemistry among the group V elements and their pseudo‐homologue protactinium are due to the increasing influence of relativistic effects as Z increases from niobium to protactinium.

Authors:
ORCiD logo [1];  [1]; ORCiD logo [2]
+ Show Author Affiliations
  1. Chemical Sciences and Engineering Division Argonne National Laboratory 60439 Argonne IL USA
  2. Univ. Lille CNRS UMR 8523 ‐ PhLAM ‐ Physique des Lasers Atomes et Molécules 59000 Lille France
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1401710
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
European Journal of Inorganic Chemistry
Additional Journal Information:
Journal Name: European Journal of Inorganic Chemistry Journal Volume: 2016 Journal Issue: 35; Journal ID: ISSN 1434-1948
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Wilson, Richard E., De Sio, Stéphanie, and Vallet, Valerie. Structural and Electronic Properties of Fluoride Complexes of Nb V , Ta V , and Pa V : The Influence of Relativistic Effects on Group V Elements. Germany: N. p., 2016. Web. doi:10.1002/ejic.201600981.
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Wilson, Richard E., De Sio, Stéphanie, & Vallet, Valerie. Structural and Electronic Properties of Fluoride Complexes of Nb V , Ta V , and Pa V : The Influence of Relativistic Effects on Group V Elements. Germany. https://doi.org/10.1002/ejic.201600981
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Wilson, Richard E., De Sio, Stéphanie, and Vallet, Valerie. Fri . "Structural and Electronic Properties of Fluoride Complexes of Nb V , Ta V , and Pa V : The Influence of Relativistic Effects on Group V Elements". Germany. https://doi.org/10.1002/ejic.201600981.
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@article{osti_1401710,
title = {Structural and Electronic Properties of Fluoride Complexes of Nb V , Ta V , and Pa V : The Influence of Relativistic Effects on Group V Elements},
author = {Wilson, Richard E. and De Sio, Stéphanie and Vallet, Valerie},
abstractNote = {Aqueous fluorido complexes of niobium and tantalum were studied by using synchrotron‐based extended X‐ray absorption spectroscopy (EXAFS) as model systems for comparison of the structural and coordination chemistry of the group V metals Nb, Ta, and their pseudo‐homologue Pa V . The EXAFS measurements indicate differences in the coordination chemistry of Nb and Ta in these systems that were not intuitively based on their similar charge and ionic radii. The Ta speciation is dominated by six‐ and seven‐coordinate fluorido complexes, while the chemical speciation of Nb under the same conditions is dominated by its hydrolyzed oxyfluoride complexes. Quantum chemical computations were performed to more fully describe these observations, and these results are compared to our earlier study on the fluorido complexes of protactinium. Computations performed with and without the inclusion of scalar relativistic effects reveal that the differences in chemistry among the group V elements and their pseudo‐homologue protactinium are due to the increasing influence of relativistic effects as Z increases from niobium to protactinium.},
doi = {10.1002/ejic.201600981},
journal = {European Journal of Inorganic Chemistry},
number = 35,
volume = 2016,
place = {Germany},
year = {Fri Nov 18 00:00:00 EST 2016},
month = {Fri Nov 18 00:00:00 EST 2016}
}
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https://doi.org/10.1002/ejic.201600981
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