The Interpretation of Sulfur K-Edge XANES Spectra: A Case Study on Thiophenic and Aliphatic Sulfur Compounds

Sulfur K-edge XANES has been measured for three sulfur model compounds, dibenzothiophene, dibenzothiophene sulfone, and aliphatic sulfur (dl-methionine). The spectra have been simulated with Density Functional Theory (DFT) by using a number of methods, including the half-core-hole approximation. Dip...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2009-03, Vol.113 (12), p.2750-2756
Main Authors: Mijovilovich, A, Pettersson, L. G. M, Mangold, S, Janousch, M, Susini, J, Salome, M, de Groot, F. M. F, Weckhuysen, B. M
Format: Article
Language:English
Subjects:
A: Kinetics, Spectroscopy
Methionine - chemistry
Models, Molecular
Spectrum Analysis
Sulfur Compounds - chemistry
Thiophenes - chemistry
X-Rays
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Summary:Sulfur K-edge XANES has been measured for three sulfur model compounds, dibenzothiophene, dibenzothiophene sulfone, and aliphatic sulfur (dl-methionine). The spectra have been simulated with Density Functional Theory (DFT) by using a number of methods, including the half-core-hole approximation. Dipole transition elements were calculated and the transitions were convoluted with linearly increasing Gaussian functions in the first 20 eV of the near-edge region. In the case of dibenzothiophene, relaxation of the first excited states in the presence of the core-hole gave a further improvement. The theoretical results reproduce well the features of the spectra and give insight in the relation between geometric structure and molecular orbitals. Though dl-methionine and dibenzothiophene show a similar sharp rise of the white line, their molecular levels are quite different, pointing out the difficulties in finding useful “fingerprints” in the spectra for specific compounds.
ISSN:1089-5639
1520-5215
DOI:10.1021/jp806823c