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Probing the potential energy surface by highresolution x-ray absorption spectroscopy: The umbrella motion of the coreexcited CH3 free radical
ISMN-CNR, Sez. Roma1, P.le A. Moro 5, I-00185 Roma, Italy and TASC-CNR, Area Science Park, Basovizza, I-34012 Trieste, Italy.
LIXAM-CNRS, F-91898 Orsay-Cedex, France.
Sincrotrone Trieste, Area Science Park, I-34012 Basovizza, Trieste, Italy.
Linköping University, Department of Physics, Chemistry and Biology, Computational Physics . Linköping University, The Institute of Technology.
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2007 (English)In: Physical Review. A, ISSN 1050-2947 (print), 1094-1622 (online), Vol. 76, no 2, 124305- p.Article in journal (Refereed) Published
Abstract [en]

A detailed study of the umbrellalike vibration in inner-shell spectroscopy is presented. The high-resolution x-ray absorption spectrum for the lowest lying core excitation of the CH3 free radical was recorded. High quality potential energy surfaces (PES) for the initial and final states of the transition were calculated as a function of the symmetrical stretching and the umbrella deformation coordinates. The strong anharmonicity along the umbrella coordinate in the double-well region of the PES of the core excited state has a strong effect on the bending vibrational progressions. The excellent agreement between the experiment and theory allows an accurate spectroscopic characterization of the vibrational structure of the electronic transition, and the estimation of the umbrella inversion time of 149  fs.

Place, publisher, year, edition, pages
2007. Vol. 76, no 2, 124305- p.
Keyword [en]
free radicals, molecular configurations, optical rotation, organic compounds, potential energy surfaces, vibrational states, X-ray absorption spectra
National Category
Physical Sciences
URN: urn:nbn:se:liu:diva-12686DOI: 10.1103/PhysRevA.76.022509OAI: diva2:16860
Available from: 2007-10-30 Created: 2007-10-30 Last updated: 2009-04-23Bibliographically 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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Ekström, Ulf
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