We report unambiguous experimental and theoretical evidence of intramolecular photoelectron diffraction in the collective vibrational excitation that accompanies high-energy photoionization of gas-phase CF4, BF3, and CH4 from the 1s orbital of the central atom. We show that the ratios between vibrationally resolved photoionization cross sections (v-ratios) exhibit pronounced oscillations as a function of photon energy, which is the fingerprint of electron diffraction by the surrounding atomic centers. This interpretation is supported by the excellent agreement between first-principles static-exchange and time-dependent density functional theory calculations and high resolution measurements, as well as by qualitative agreement at high energies with a model in which atomic displacements are treated to first order of perturbation theory. The latter model allows us to rationalize the results for all the v-ratios in terms of a generalized v-ratio, which contains information on the structure of the above three molecules and the corresponding molecular cations. A fit of the measured v-ratios to a simple formula based on this model suggests that the method could be used to obtain structural information of both neutral and ionic molecular species.
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28 September 2013
Research Article|
September 27 2013
Intramolecular photoelectron diffraction in the gas phase
K. Ueda;
K. Ueda
a)
1Institute of Multidisciplinary Research for Advanced Materials,
Tohoku University
, Sendai 980-8577, Japan
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C. Miron;
C. Miron
2Synchrotron SOLEIL,
L'Orme des Merisiers
, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette Cedex, France
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E. Plésiat;
E. Plésiat
3Departamento de Química, Módulo 13,
Universidad Autónoma de Madrid
, 28049 Madrid, Spain
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L. Argenti;
L. Argenti
3Departamento de Química, Módulo 13,
Universidad Autónoma de Madrid
, 28049 Madrid, Spain
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M. Patanen;
M. Patanen
2Synchrotron SOLEIL,
L'Orme des Merisiers
, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette Cedex, France
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K. Kooser;
K. Kooser
4Department of Physics and Astronomy,
University of Turku
, 20014 Turku, Finland
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D. Ayuso;
D. Ayuso
3Departamento de Química, Módulo 13,
Universidad Autónoma de Madrid
, 28049 Madrid, Spain
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S. Mondal;
S. Mondal
1Institute of Multidisciplinary Research for Advanced Materials,
Tohoku University
, Sendai 980-8577, Japan
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M. Kimura;
M. Kimura
1Institute of Multidisciplinary Research for Advanced Materials,
Tohoku University
, Sendai 980-8577, Japan
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K. Sakai;
K. Sakai
1Institute of Multidisciplinary Research for Advanced Materials,
Tohoku University
, Sendai 980-8577, Japan
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O. Travnikova;
O. Travnikova
2Synchrotron SOLEIL,
L'Orme des Merisiers
, Saint-Aubin, BP 48, 91192 Gif-sur-Yvette Cedex, France
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A. Palacios;
A. Palacios
3Departamento de Química, Módulo 13,
Universidad Autónoma de Madrid
, 28049 Madrid, Spain
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P. Decleva;
P. Decleva
5Dipartimento di Scienze Chimiche,
Universita' di Trieste
, 34127 Trieste, and CNR-IOM, Trieste, Italy
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E. Kukk;
E. Kukk
4Department of Physics and Astronomy,
University of Turku
, 20014 Turku, Finland
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a)
Electronic mail: [email protected]
b)
Electronic mail: [email protected]
J. Chem. Phys. 139, 124306 (2013)
Article history
Received:
May 27 2013
Accepted:
August 05 2013
Citation
K. Ueda, C. Miron, E. Plésiat, L. Argenti, M. Patanen, K. Kooser, D. Ayuso, S. Mondal, M. Kimura, K. Sakai, O. Travnikova, A. Palacios, P. Decleva, E. Kukk, F. Martín; Intramolecular photoelectron diffraction in the gas phase. J. Chem. Phys. 28 September 2013; 139 (12): 124306. https://doi.org/10.1063/1.4820814
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