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The umbrella motion of core-excited CH3 and CD3 methyl radicals
Linköping University, Department of Physics, Chemistry and Biology, Computational Physics. Linköping University, The Institute of Technology.
Institute of Chemical Physical Processes, CNR, Pisa, Italy.
Istituto per lo Studio dei Materiali Nanostrutturati, CNR, Roma, Italy and TASC-CNR, Area Science Park, Trieste, Italy.
CNRS, Université Paris-Sud, Orsay-Cedex, France.
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2008 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 128, no 4, 044302-1-044302-11 p.Article in journal (Refereed) Published
Abstract [en]

An accurate experimental and theoretical study of the lowest core excitationof CH3 and CD3 methyl radicals is presented. The complexvibrational structure of the lowest band of the x-ray absorptionspectrum (XAS) is due to the large variation of themolecular geometry, which is planar in the ground state andpyramidal in the core-excited state. The XAS spectra of thetwo radicals were recorded at high resolution and assigned bytheoretical simulations of the spectra, taking into account the couplingof symmetrical stretching and symmetrical bending (umbrellalike) deformations of theradicals. An excellent agreement between experimental and theoretical spectral profilesallowed us to accurately characterize the vibrational structure of theelectronic transition. The similarities, as well as the differences, ofthe peculiar vibrational progression observed for the two radicals areexplained by the strong anharmonicity along the umbrella coordinate andby the isotopic variation, leading to a different probing ofthe double-well potential energy surface of the core excited stateduring the nuclear motion.

Place, publisher, year, edition, pages
College Park, MD United States: American Institute of Physics (AIP), 2008. Vol. 128, no 4, 044302-1-044302-11 p.
Keyword [en]
excited states, free radicals, ground states, molecular configurations, organic compounds, potential energy surfaces, vibrational states, X-ray scattering
National Category
Natural Sciences
URN: urn:nbn:se:liu:diva-12687DOI: 10.1063/1.2822246ISI: 000252821200025OAI: diva2:16861
Available from: 2007-10-30 Created: 2007-10-30 Last updated: 2014-01-13Bibliographically approved
In thesis
1. Time-dependent molecular properties in the optical and x-ray regions
Open this publication in new window or tab >>Time-dependent molecular properties in the optical and x-ray regions
2007 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Time-dependent molecular properties are important for the experimental characterization of molecular materials. We show how these properties can be calculated, for optical and x-ray frequencies, using novel quantum chemical methods. For xray absorption there are important relativistic effects appearing, due to the high velocity electrons near the atomic nuclei. These effects are treated rigorously within the four-component static exchange approximation. We also show how electron correlation can be taken into account in the calculation of x-ray absorption spectra, in time-dependent density functional theory based on the complex polarization propagator approach. The methods developed have been applied to systems of experimental interest|molecules in the gas phase and adsorbed on metal surfaces. The effects of molecular vibrations have been take into account both within and beyond the harmonic approximation.

Place, publisher, year, edition, pages
Institutionen för fysik, kemi och biologi, 2007
Linköping Studies in Science and Technology. Dissertations, ISSN 0345-7524 ; 1131
Quantum chemistry, molecular physics, x-ray spectroscopy, relativity
National Category
Other Physics Topics
urn:nbn:se:liu:diva-10125 (URN)978-91-85895-88-5 (ISBN)
Public defence
2007-10-23, Planck, Fysikhuset, Campus Valla, Linköpings universitet, Linköping, 10:15 (English)
Available from: 2007-10-30 Created: 2007-10-30 Last updated: 2009-04-26

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