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Title: Spectroscopic analysis of small organic molecules: A comprehensive near-edge x-ray-absorption fine-structure study of C{sub 6}-ring-containing molecules

Abstract

We report high-resolution C 1s near-edge x-ray-absorption fine-structure (NEXAFS) spectra of the C{sub 6}-ring-containing molecules benzene (C{sub 6}H{sub 6}), 1,3- and 1,4-cyclohexadiene (C{sub 6}H{sub 8}), cyclohexene (C{sub 6}H{sub 10}), cyclohexane (C{sub 6}H{sub 12}), styrene (C{sub 8}H{sub 8}), and ethylbenzene (C{sub 8}H{sub 10}) which allow us to examine the gradual development of delocalization of the corresponding {pi} electron systems. Due to the high experimental resolution, vibrational progressions can be partly resolved in the spectra. The experimental spectra are compared with theoretical NEXAFS spectra obtained from density-functional theory calculations where electronic final-state relaxation is accounted for. The comparison yields very good agreement between theoretical spectra and experimental results. In all cases, the spectra can be described by excitations to {pi}*- and {sigma}*-type final-state orbitals with valence character, while final-state orbitals of Rydberg character make only minor contributions. The lowest C 1s{yields}1{pi}* excitation energy is found to agree in the (experimental and theoretical) spectra of all molecules except for 1,3-cyclohexadiene (C{sub 6}H{sub 8}) where an energy smaller by about 0.6 eV is obtained. The theoretical analysis can explain this result by different binding properties of this molecule compared to the others.

Authors:
; ; ; ; ; ; ;  [1]
  1. Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin (Germany)
Publication Date:
OSTI Identifier:
20783213
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 124; Journal Issue: 3; Other Information: DOI: 10.1063/1.2139674; (c) 2006 American Institute of Physics; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTRA; ABSORPTION SPECTROSCOPY; BENZENE; COMPARATIVE EVALUATIONS; CYCLOHEXANE; DENSITY FUNCTIONAL METHOD; EXCITATION; FINE STRUCTURE; MOLECULAR STRUCTURE; PHOTOCHEMISTRY; STYRENE; X-RAY SPECTROSCOPY

Citation Formats

Kolczewski, C, Puettner, R, Martins, M, Schlachter, A S, Snell, G, Sant'Anna, M M, Hermann, K, Kaindl, G, Freie Universitaet Berlin, Institut fuer Experimentalphysik, Arnimallee 14, 14195 Berlin, Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, and Freie Universitaet Berlin, Institut fuer Experimentalphysik, Arnimallee 14, 14195 Berlin. Spectroscopic analysis of small organic molecules: A comprehensive near-edge x-ray-absorption fine-structure study of C{sub 6}-ring-containing molecules. United States: N. p., 2006. Web. doi:10.1063/1.2139674.
Kolczewski, C, Puettner, R, Martins, M, Schlachter, A S, Snell, G, Sant'Anna, M M, Hermann, K, Kaindl, G, Freie Universitaet Berlin, Institut fuer Experimentalphysik, Arnimallee 14, 14195 Berlin, Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, & Freie Universitaet Berlin, Institut fuer Experimentalphysik, Arnimallee 14, 14195 Berlin. Spectroscopic analysis of small organic molecules: A comprehensive near-edge x-ray-absorption fine-structure study of C{sub 6}-ring-containing molecules. United States. https://doi.org/10.1063/1.2139674
Kolczewski, C, Puettner, R, Martins, M, Schlachter, A S, Snell, G, Sant'Anna, M M, Hermann, K, Kaindl, G, Freie Universitaet Berlin, Institut fuer Experimentalphysik, Arnimallee 14, 14195 Berlin, Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin, and Freie Universitaet Berlin, Institut fuer Experimentalphysik, Arnimallee 14, 14195 Berlin. 2006. "Spectroscopic analysis of small organic molecules: A comprehensive near-edge x-ray-absorption fine-structure study of C{sub 6}-ring-containing molecules". United States. https://doi.org/10.1063/1.2139674.
@article{osti_20783213,
title = {Spectroscopic analysis of small organic molecules: A comprehensive near-edge x-ray-absorption fine-structure study of C{sub 6}-ring-containing molecules},
author = {Kolczewski, C and Puettner, R and Martins, M and Schlachter, A S and Snell, G and Sant'Anna, M M and Hermann, K and Kaindl, G and Freie Universitaet Berlin, Institut fuer Experimentalphysik, Arnimallee 14, 14195 Berlin and Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720 and Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720 and Advanced Light Source, Lawrence Berkeley National Laboratory, Berkeley, California 94720 and Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195 Berlin and Freie Universitaet Berlin, Institut fuer Experimentalphysik, Arnimallee 14, 14195 Berlin},
abstractNote = {We report high-resolution C 1s near-edge x-ray-absorption fine-structure (NEXAFS) spectra of the C{sub 6}-ring-containing molecules benzene (C{sub 6}H{sub 6}), 1,3- and 1,4-cyclohexadiene (C{sub 6}H{sub 8}), cyclohexene (C{sub 6}H{sub 10}), cyclohexane (C{sub 6}H{sub 12}), styrene (C{sub 8}H{sub 8}), and ethylbenzene (C{sub 8}H{sub 10}) which allow us to examine the gradual development of delocalization of the corresponding {pi} electron systems. Due to the high experimental resolution, vibrational progressions can be partly resolved in the spectra. The experimental spectra are compared with theoretical NEXAFS spectra obtained from density-functional theory calculations where electronic final-state relaxation is accounted for. The comparison yields very good agreement between theoretical spectra and experimental results. In all cases, the spectra can be described by excitations to {pi}*- and {sigma}*-type final-state orbitals with valence character, while final-state orbitals of Rydberg character make only minor contributions. The lowest C 1s{yields}1{pi}* excitation energy is found to agree in the (experimental and theoretical) spectra of all molecules except for 1,3-cyclohexadiene (C{sub 6}H{sub 8}) where an energy smaller by about 0.6 eV is obtained. The theoretical analysis can explain this result by different binding properties of this molecule compared to the others.},
doi = {10.1063/1.2139674},
url = {https://www.osti.gov/biblio/20783213}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 3,
volume = 124,
place = {United States},
year = {Sat Jan 21 00:00:00 EST 2006},
month = {Sat Jan 21 00:00:00 EST 2006}
}