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Role of the recoil effect on two-center interference in x-ray photoionization
KTH, School of Biotechnology (BIO).
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2006 (English)In: Chemical Physics, ISSN 0301-0104, E-ISSN 1873-4421, Vol. 329, no 1-3, 329-337 p.Article in journal (Refereed) Published
Abstract [en]

X-ray photoelectron spectra of the N-2 molecule are studied both experimentally and theoretically in the extended energy region up to 1 keV. The ratio of the photoionization cross sections for the gerade and ungerade core levels displays a modulation in the high energy region caused by the two-center interference, as predicted by Cohen and Fano (CF) in 1966. The physical background of this CF effect is the same as in Young's double-slit experiment. We have found that the interference pattern deviates significantly from the CF prediction. The origin of such a breakdown of the CF formula is the scattering of the photoelectron inside the molecule and the momentum transfer from the emitted fast photoelectron to the nuclei. Usually the recoil effect is small. We show that the electron recoil strongly affects the two-center interference pattern. Both stationary and dynamical aspects of the recoil effect shed light on the role of the momentum exchange in the two-center interference.

Place, publisher, year, edition, pages
2006. Vol. 329, no 1-3, 329-337 p.
Keyword [en]
X-ray photoelectron spectroscopy, recoil, interference
National Category
Theoretical Chemistry
URN: urn:nbn:se:kth:diva-5557DOI: 10.1016/j.chemphys.2006.06.022ISI: 000241574500035ScopusID: 2-s2.0-33749537232OAI: diva2:9958

Uppdaterad från manuskript till artikel: 20100910 Tidigare titel: Role of the recoil effect on two-center interference in x-ray photoionization of N$_2$ molecules QC 20100910

Available from: 2006-04-05 Created: 2006-04-05 Last updated: 2016-04-21Bibliographically approved
In thesis
1. Nuclear Dynamics in X-ray Absorption and Raman Scattering
Open this publication in new window or tab >>Nuclear Dynamics in X-ray Absorption and Raman Scattering
2006 (English)Doctoral thesis, comprehensive summary (Other scientific)
Abstract [en]

This thesis presents theoretical studies of several x-ray spectroscopies - x-ray absorption, x-ray photoelectron emission, radiative and non-radiative resonant Raman scattering spectroscopy. The main focus point is investigating the influence of nuclear dynamics on these spectra for a variety of small molecules - naphthalene, biphenyl, ethylene, the water dimer, HCl, CO. The theoretical tools used consist of the basic equations of the relevant x-ray spectroscopy. Wave packet methods are also used. The molecular parameters needed for our simulations are obtained through suitable quantum chemical calculations, based on either wave function or density functional methods. Our simulations are compared to experimental data, where available.

Simulations of x-ray absorption and x-ray photoionization spectra for naphthalene and biphenyl show that the spectral shapes are heavily influenced by the joint effect of two factors -- chemical shifts and excitations of vibrational progression. Comparison between the two molecules and also comparison to a reference case -- benzene, provides useful insight into the molecular behavior under core excitation.

In a further step, we consider the O1s x-ray photoelectron spectrum of the water dimer. A substantial broadening of the two bands originating from the donor and the acceptor oxygen is found. It is caused by excitations of soft intermolecular vibrational modes, associated with the hydrogen bond.

Another strong influence of the nuclear dynamics is clearly seen in the resonant x-ray Raman scattering of HCl. Vibrational collapse is observed experimentally and confirmed theoretically for distinctive situations. This effect allows to eliminate completely the vibrational broadening, and hence, considerably increase the spectral resolution.

We considered also the vibrational dynamics in resonant soft x-ray Raman scattering from ethylene. The importance of vibronic coupling and symmetry effects is discussed and emphasized. We obtained excellent agreement with the experimental data.

We predict an interference effect in the resonant Auger scattering from fixed-in-space molecules. By exciting a molecule to a dissociative state and measuring the angular distribution of the Auger electrons in coincidence with the molecular ion, one can observe this effect. The interference pattern can be used after Fourier transformation for extracting structural data about the studied system.

We have found that two-center interference leads to an enhancement of the recoil effect.

Finally, it is shown that core excitation to doubly-excited dissociative Pi state is accompanied by Doppler splitting of the atomic peak in resonant Auger scattering from carbon monoxide.

Place, publisher, year, edition, pages
Stockholm: KTH, 2006. viii, 57 p.
Theses in philosophy from the Royal Institute of Technology, ISSN 1650-8831
x-ray scattering, theory, simulations, recoil, Doppler effect, nuclear dynamics, Auger, XPS
National Category
Theoretical Chemistry
urn:nbn:se:kth:diva-3902 (URN)91-7178-276-1 (ISBN)
Public defence
2006-04-21, FA 32, AlbaNova, Roslagstullsbacken 21, 09:00
QC 20100910Available from: 2006-04-05 Created: 2006-04-05 Last updated: 2010-09-10Bibliographically approved

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