| 1. |
- Martensson, Nils, et al.
(författare)
-
On the relation between X-ray Photoelectron Spectroscopy and XAFS
- 2013
-
Ingår i: 15th International Conference On X-Ray Absorption Fine Structure (XAFS15). - : IOP Publishing.
-
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.
|
|
| 2. |
- Söderström, Johan, et al.
(författare)
-
Nonstoichiometric Intensities in Core Photoelectron Spectroscopy
- 2012
-
Ingår i: Physical Review Letters. - 0031-9007 .- 1079-7114. ; 108:19, s. 193005-
-
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.
|
|
| 3. |
- Harnes, J., et al.
(författare)
-
Size of Free Neutral CO(2) Clusters from Carbon 1s Ionization Energies
- 2011
-
Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 115:38, s. 10408-10415
-
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.
|
|
| 4. |
- Harnes, J., et al.
(författare)
-
The structure of mixed methanol/chloroform clusters from core-level photoelectron spectroscopy and modeling
- 2011
-
Ingår i: New Journal of Chemistry. - : Royal Society of Chemistry (RSC). - 1144-0546 .- 1369-9261. ; 35:11, s. 2564-2572
-
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.
|
|
| 5. |
- Patanen, M., et al.
(författare)
-
Laboratory-frame electron angular distributions : Probing the chemical environment through intramolecular electron scattering
- 2013
-
Ingår i: Physical Review A. Atomic, Molecular, and Optical Physics. - 1050-2947 .- 1094-1622. ; 87:6, s. 063420-
-
Tidskriftsartikel (refereegranskat)abstract
- Carbon 1s photoelectron asymmetry parameters beta for the chlorinated and the methyl carbon atom of CH3CH2Cl, CH3CHCl2, and CH3CCl3 have been measured using synchrotron radiation in the 340-600 eV energy range. We provide experimental evidence that the intramolecular scattering strongly affects beta values, even far from the ionization threshold. The results are in agreement with B-spline density functional theory calculations, making it possible to single out the behavior of the various continuum partial waves. We conclude that the intramolecular scattering makes electron angular distributions sensitive to the chemical environment, even in isolated gas phase molecules.
|
|
| 6. |
- Thomas, T. D., et al.
(författare)
-
Valence photoelectron spectroscopy of N-2 and CO: Recoil-induced rotational excitation, relative intensities, and atomic orbital composition of molecular orbitals
- 2010
-
Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 133:17
-
Tidskriftsartikel (refereegranskat)abstract
- Recoil-induced rotational excitation accompanying photoionization has been measured for the X, A, and B states of N-2(+) and CO+ over a range of photon energies from 60 to 900 eV. The mean recoil excitation increases linearly with the kinetic energy of the photoelectron, with slopes ranging from 0.73 x 10(-5) to 1.40 x 10(-5). These slopes are generally (but not completely) in accord with a simple model that treats the electrons as if they were emitted from isolated atoms. This treatment takes into account the atom from which the electron is emitted, the molecular-frame angular distribution of the electron, and the dependence of the photoelectron cross section on photon energy, on atomic identity, and on the type of atomic orbital from which the electron is ejected. These measurements thus provide a tool for investigating the atomic orbital composition of the molecular orbitals. Additional insight into this composition is obtained from the relative intensities of the various photolines in the spectrum and their variation with photon energy. Although there are some discrepancies between the predictions of the model and the observations, many of these can be understood qualitatively from a comparison of atomic and molecular wavefunctions. A quantum-mechanical treatment of recoil-induced excitation predicts an oscillatory variation with photon energy of the excitation. However, the predicted oscillations are small compared with the uncertainties in the data, and, as a result, the currently available results cannot provide confirmation of the quantum-mechanical theory. (C) 2010 American Institute of Physics. [doi:10.1063/1.3503658]
|
|
