| 1. |
- Martensson, Nils, et al.
(författare)
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On the relation between X-ray Photoelectron Spectroscopy and XAFS
- 2013
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Ingår i: 15th International Conference On X-Ray Absorption Fine Structure (XAFS15). - : IOP Publishing.
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Konferensbidrag (refereegranskat)abstract
- XAFS and X-ray Photoelectron Spectroscopy (XPS) are element specific techniques used in a great variety of research fields. The near edge regime of XAFS provides information on the unoccupied electronic states of a system. For the detailed interpretation of the XAFS results, input from XPS is crucial. The combination of the two techniques is also the basis for the so called core-hole clock technique. One of the important aspects of photoelectron spectroscopy is its chemical sensitivity and that one can obtain detailed information about the composition of a sample. We have for a series of carbon based model molecules carefully investigated the relationship between core level photoelectron intensities and stoichiometry. We find strong EXAFS-like modulations of the core ionization cross sections as function of photon energy and that the intensities at high photon energies converge towards values that do not correspond to the stoichiometric ratios. The photoelectron intensities are dependent on the local molecular structure around the ionized atoms. These effects are well described by molecular calculations using multiple scattering theory and by considering the effects due to monopole shake-up and shake-off as well as to intramolecular inelastic scattering processes.
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| 2. |
- Söderström, Johan, et al.
(författare)
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Nonstoichiometric Intensities in Core Photoelectron Spectroscopy
- 2012
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Ingår i: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 108:19, s. 193005-
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Tidskriftsartikel (refereegranskat)abstract
- X-ray photoemission spectroscopy is used in a great variety of research fields; one observable is the sample's stoichiometry. The stoichiometry can be deduced based on the expectation that the ionization cross sections for innershell orbitals are independent of the molecular composition. Here we used chlorine-substituted ethanes in the gas phase to investigate the apparent carbon stoichiometry. We observe a nonstoichiometric ratio for a wide range of photon energies, the ratio exhibits x-ray-absorption fine structure spectroscopy (EXAFS)-like oscillations and hundreds of eV above the C1s ionization approaches a value far from 1. These effects can be accounted for by considering the scattering of the outgoing photoelectron, which we model by multiple-scattering EXAFS calculations, and by considering the effects of losses due to monopole shakeup and shakeoff and to intramolecular inelastic scattering processes.
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| 3. |
- Abu-samha, M, et al.
(författare)
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The local structure of small water clusters : imprints on the core-level photoelectron spectrum
- 2009
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Ingår i: Journal of Physics B. - : IOP Publishing. - 0953-4075 .- 1361-6455. ; 42:5, s. 055201-
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Tidskriftsartikel (refereegranskat)abstract
- We report on an O 1s photoelectron-spectroscopy study of small neutral water clusters produced by adiabatic expansion. The photoelectron spectra were acquired under two different experimental conditions. At intermediate resolution, the cluster signal was characterized by a very broad O 1s peak with a flat top. In the second set of measurements, resolution was significantly increased at the cost of lower count rates. The cluster signal was now partly resolved into a bimodal structure. Extensive theoretical calculations were undertaken to facilitate an interpretation of the spectrum. These results suggest that the bimodal feature may be ascribed to ionization of water molecules in different hydrogen-bonding configurations, more specifically, molecules characterized by donation of either one or both hydrogen atoms in H-bonding.
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| 4. |
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| 5. |
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| 6. |
- Giertz, A., et al.
(författare)
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Vibrationally resolved photoelectron spectra of the carbon 1s and nitrogen 1s shells in hydrogen cyanide
- 2002
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Ingår i: Chemical Physics. - 0301-0104. ; 277:1, s. 83-90
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Tidskriftsartikel (refereegranskat)abstract
- Vibrational structures of the C1s and N1s photoelectron spectra of gas-phase HCN have been investigated using monochromated third-generation synchrotron radiation. Both spectra exhibit resolved fine structure associated with several vibrationally excited states. In the C1s spectrum a single vibrational progression is observed, while the N1s spectrum is more complex. High-level ab initio calculations were performed to simulate the spectra and the agreement with the experimental results is good. Based on the calculations, the C1s ionisation is found to induce vibrations solely in the C≡N stretching mode with an energy of 280 meV, while the N1s ionisation generates vibrations also in the C-H stretching mode with an energy of about 387 meV, as well as combinations of these two modes.
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| 7. |
- Harnes, J., et al.
(författare)
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Neutral CH3Cl and CH3Br clusters studied by X-ray photoelectron spectroscopy and modeling : Insight to intermolecular interactions and structure
- 2008
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Ingår i: Journal of Electron Spectroscopy and Related Phenomena. - : Elsevier BV. - 0368-2048 .- 1873-2526. ; 166, s. 53-64
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Tidskriftsartikel (refereegranskat)abstract
- Single-component clusters of methyl chloride and methyl bromide have been produced by adiabatic expansion and their C 1s, Cl 2p and Br 3d photoelectron spectra recorded using synchrotron radiation and a high-resolution electron analyzer. The experimentally observed cluster-to-monomer shifts in core-level ionization energies are interpreted in terms of theoretical models based on molecular dynamics (MD) in conjunction with polarizable force fields developed and validated in the course of this work. MD simulations have also been used to explore the global and local structure of the clusters, providing evidence for a predominance of anti-parallel, head-to-tail arrangement of neighboring molecules. Whereas the cluster-to-monomer shifts are strongly dominated by polarization effects, the polarization contribution is very similar for ionization of carbon and the halogen, respectively. The difference in cluster shifts between the two ionization sites within the same molecule, C vs. Cl or C vs. Br, is thus determined by permanent electrostatic moments, i.e. the magnitude and direction of the permanent dipole moment and the local alignment of dipoles.
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| 8. |
- Harnes, J., et al.
(författare)
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Size of Free Neutral CO(2) Clusters from Carbon 1s Ionization Energies
- 2011
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Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 115:38, s. 10408-10415
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Tidskriftsartikel (refereegranskat)abstract
- Free neutral CO(2) clusters were produced by adiabatic expansion and characterized by carbon 1s (C1s) photoelectron spectroscopy using synchrotron radiation. The shift in C1s ionization energy (IE) between the cluster and the monomer, i.e., Delta IE = IE(cluster) - IE(monomer), was found to vary systematically with the experimental conditions. A functional relationship is established between the mean cluster size in the beam, < N >, and Delta IE, in good agreement with theoretical calculations of shifts in ionization energy for model clusters. This makes it possible to use core-level photoelectron spectroscopy to monitor the mean cluster size and also to estimate < N > from expansion conditions.
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| 9. |
- Harnes, J., et al.
(författare)
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The structure of mixed methanol/chloroform clusters from core-level photoelectron spectroscopy and modeling
- 2011
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Ingår i: New Journal of Chemistry. - : Royal Society of Chemistry (RSC). - 1144-0546 .- 1369-9261. ; 35:11, s. 2564-2572
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Tidskriftsartikel (refereegranskat)abstract
- Mixed neutral molecular clusters have been produced by co-expansion of chloroform and methanol and characterized by carbon 1s photoelectron spectroscopy and theoretical modeling. The produced clusters are in the range 50-150 molecules and the clusters are not homogeneously mixed: chloroform is enriched in the bulk and methanol is found on or close to the surface. This is based on evidence from photoelectron depth profiling and molecular dynamics simulations of mixed clusters. The simulations suggest that methanol forms cyclic or linear oligomers in the surface layers of the mixed clusters. From thermodynamic models, the enrichment of methanol on the cluster surface can be rationalized from the difference in surface tension between the two pure components, which is connected to the qualitative differences in the respective bonding patterns.
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| 10. |
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