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Local structure of reaction intermediates probed by time-resolved x-ray absorption near edge structure spectroscopy

Local structure of reaction intermediates probed by time-resolved x-ray absorption near edge structure spectroscopy
Local structure of reaction intermediates probed by time-resolved x-ray absorption near edge structure spectroscopy
A method for the analysis of time-resolved x-ray absorption near edge structure XANES spectra
is proposed. It combines principal component analysis of the series of experimental spectra,
multidimensional interpolation of theoretical XANES as a function of structural parameters, and ab
initio XANES calculations. It allows to determine the values of structural parameters for
intermediates of chemical reactions and the concentrations of different states as a function of time.
This approach is tested using numerically generated data and its possibilities and limitations are
discussed. The application of this method to a reaction with methylrhenium trioxide catalyst in
solution, for which experimental data were measured using stopped-flow energy-dispersive x-ray
absorption spectroscopy technique, is demonstrated. Possibilities and limitations of this
experimental technique are also discussed.
ab initio calculations, catalysis, interpolation, principal component analysis, reaction kinetics theory, spectrochemical analysis, time resolved spectra, XANES, x-ray chemical analysis
0021-9606
174508
Smolentsev, G.
9bcd1f06-a123-4e70-b712-c497f668aefb
Guilera, G.
394209e2-2aa6-4da9-9aa7-fb0e25366d3b
Tromp, M.
48c1ebbb-579c-42b6-83bb-7188c668b322
Pascarelli, S.
ce345fc4-e758-4c49-9da1-323ef3f06500
Soldatov, A.V.
b0476a50-934e-43fa-9136-3ee567f0e7c8
Smolentsev, G.
9bcd1f06-a123-4e70-b712-c497f668aefb
Guilera, G.
394209e2-2aa6-4da9-9aa7-fb0e25366d3b
Tromp, M.
48c1ebbb-579c-42b6-83bb-7188c668b322
Pascarelli, S.
ce345fc4-e758-4c49-9da1-323ef3f06500
Soldatov, A.V.
b0476a50-934e-43fa-9136-3ee567f0e7c8

Smolentsev, G., Guilera, G., Tromp, M., Pascarelli, S. and Soldatov, A.V. (2009) Local structure of reaction intermediates probed by time-resolved x-ray absorption near edge structure spectroscopy. Journal of Chemical Physics, 130, 174508. (doi:10.1063/1.3125940).

Record type: Article

Abstract

A method for the analysis of time-resolved x-ray absorption near edge structure XANES spectra
is proposed. It combines principal component analysis of the series of experimental spectra,
multidimensional interpolation of theoretical XANES as a function of structural parameters, and ab
initio XANES calculations. It allows to determine the values of structural parameters for
intermediates of chemical reactions and the concentrations of different states as a function of time.
This approach is tested using numerically generated data and its possibilities and limitations are
discussed. The application of this method to a reaction with methylrhenium trioxide catalyst in
solution, for which experimental data were measured using stopped-flow energy-dispersive x-ray
absorption spectroscopy technique, is demonstrated. Possibilities and limitations of this
experimental technique are also discussed.

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More information

Published date: 7 April 2009
Keywords: ab initio calculations, catalysis, interpolation, principal component analysis, reaction kinetics theory, spectrochemical analysis, time resolved spectra, XANES, x-ray chemical analysis
Organisations: Chemistry

Identifiers

Local EPrints ID: 146117
URI: http://eprints.soton.ac.uk/id/eprint/146117
ISSN: 0021-9606
PURE UUID: 3f1df033-47a0-45d9-a268-8dc8b3a7ae5c

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Date deposited: 20 Apr 2010 15:15
Last modified: 14 Mar 2024 00:54

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Contributors

Author: G. Smolentsev
Author: G. Guilera
Author: M. Tromp
Author: S. Pascarelli
Author: A.V. Soldatov

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