| 1. |
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| 2. |
- Andersson, Tomas, et al.
(författare)
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Photon energy influence on valence photoelectron spectra of silver clusters
- 2012
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Ingår i: Journal of Physics, Conference Series. - : IOP Publishing. - 1742-6588 .- 1742-6596. ; 388:15, s. 152028-
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Tidskriftsartikel (refereegranskat)abstract
- Silver clusters in the size range of ∼102 constituent atoms have been studied using photoelectron spec-troscopy. The 5s and 4d valence bands have been probed with 40 and 60.5 eV photon energies. Differences in the valence band spectral features have been observed and are discussed in view of earlier results on copper clusters and in terms of differences in mean free path for electrons of different energies.
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| 3. |
- Andersson, Tomas, et al.
(författare)
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Plasmon single- and multi-quantum excitation in free metal clusters as seen by photoelectron spectroscopy
- 2011
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 134:9, s. 094511-
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Tidskriftsartikel (refereegranskat)abstract
- Plasmons are investigated in free nanoscale Na, Mg, and K metal clusters using synchrotron radiation-based x-ray photoelectron spectroscopy. The core levels for which the response from bulk and surface atoms can be resolved are probed over an extended binding energy range to include the plasmon loss features. In all species the features due to fundamental plasmons are identified, and in Na and K also those due to either the first order plasmon overtones or sequential plasmon excitation are observed. These features are discussed in view of earlier results for planar macroscopic samples and free clusters of the same materials.
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| 4. |
- Arion, Tiberiu, et al.
(författare)
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New insight into the Auger decay process in O-2: The coincidence perspective
- 2012
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Ingår i: Journal of Electron Spectroscopy and Related Phenomena. - : Elsevier BV. - 0368-2048 .- 1873-2526. ; 185:8-9, s. 234-243
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Tidskriftsartikel (refereegranskat)abstract
- Photoelectron-Auger electron coincidence spectroscopy is a powerful tool for the investigation of Auger decay processes with different core-ionized intermediate states. In this paper we describe an investigation into the Auger decay of the O-2 molecule, with the purpose of bringing new insight into the dynamics of the core hole decay mechanism. Using a novel experimental approach to measuring such coincidence spectra we report the highest resolution Auger spectrum of O-2 recorded hitherto. In our approach, we have combined the advantages of these coincidence spectra with the high resolution and excellent signal-to-noise ratios of non-coincident Auger spectra and a state-of-the-art fit analysis. In this way we have derived information about the potential energy curves of the final states W-3 Delta(u), B-3 Pi(g), and B' (3)Sigma(-)(u) and concluded that the corresponding Auger transitions are formed to a large part by strongly overlapping vibrational progressions. The present findings are compared to earlier results reported in the literature confirming some theoretical predictions. (C) 2012 Elsevier B.V. All rights reserved.
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| 5. |
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| 6. |
- Bergersen, Henrik, et al.
(författare)
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A photoelectron spectroscopic study of aqueous tetrabutylammonium iodide
- 2007
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Ingår i: Journal of Physics. - : IOP Publishing. - 0953-8984 .- 1361-648X. ; 19:32, s. 326101-
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Tidskriftsartikel (refereegranskat)abstract
- Photoelectron spectra of tetrabutylammonium iodide (TBAI) dissolved in water have been recorded using a novel experimental set-up, which enables photoelectron spectroscopy of volatile liquids. The set-up is described in detail. Ionization energies are reported for I− 5p, I− 4d, C 1s and N 1s. The C 1s spectrum shows evidence of inelastic scattering of the photoelectrons, that differs from the case of TBAI in formamide.
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| 7. |
- Bergersen, Henrik, et al.
(författare)
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First observation of vibrations in core-level photoelectron spectra of free neutral molecular clusters
- 2006
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Ingår i: Chemical Physics Letters. - : Elsevier BV. - 0009-2614 .- 1873-4448. ; 429:1-3, s. 109-113
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Tidskriftsartikel (refereegranskat)abstract
- Core-level photoelectron spectra of free neutral methane clusters have been recorded. These spectra exhibit well-resolved surface and bulk features as well as vibrational fine structure. The vibrational structure in the cluster signal is well reproduced by a theoretical model that assumes independent contributions from inter- and intramolecular modes. The intramolecular contribution to the vibrational line-shape is taken to be equal to that of the monomer in the gas phase, while the intermolecular part is simplified to line broadening. An estimate of the cluster size has been made on the basis of the observed surface-to-bulk intensity ratio.
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| 8. |
- Bergersen, Henrik, 1978-
(författare)
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Free Neutral Clusters and Liquids Studied by Electron Spectroscopy and Lineshape Modeling
- 2008
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The electronic and geometrical structure of free neutral clusters and liquids have been studied using synchrotron-radiation based photoelectron and Auger electron spectroscopy in combination with lineshape modeling. A novel experimental setup has been developed for studies of liquids, based on the liquid microjet technique. Theoretical lineshapes have been computed using both classical (molecular dynamics) and quantum mechanical (mainly density functional theory) methods.Clusters are finite ensembles of atoms or molecules, ranging in size from a few to several thousand atoms. Apart from being fundamentally interesting, clusters are also promising as building blocks for nano-technology. In this thesis results are presented for rare-gas and molecular clusters, ranging from weakly van-deer-Waals bonded to hydrogen bonded. It is shown that the combination of core-level photoelectron spectroscopy (XPS) and lineshape modeling can be used to estimate the sizes of clusters. A model for treating the effect of inter-molecular nuclear relaxation upon ionization is proposed. The structure of single-component molecular clusters are investigated by molecular dynamics simulations, validated against XPS data. Finally, the radial structure of a two-component molecular cluster is investigated by XPS.Liquids have been studied for centuries, but still many questions remain regarding the microscopic properties. With the recent development of the liquid microjet technique, new insight into the atomic structure can be obtained. In this thesis we study aqueous solutions using photoelectron and Auger electron spectroscopy (AES). We investigate the structure of surface active molecules by XPS, study the Auger decay after core-level ionization in aqueous potassium chloride (KCl), and follow the changes in molecular structure of glycine as a function of pH.
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| 9. |
- Bergersen, Henrik, et al.
(författare)
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Two size regimes of methanol clusters produced by adiabatic expansion
- 2006
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 125:18, s. 184303-
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Tidskriftsartikel (refereegranskat)abstract
- Free neutral methanol clusters produced by adiabatic expansion have been studied by photoelectron spectroscopy and line shape modeling. The results show that clusters belonging to two distinct size regimes can be produced by changing the expansion conditions. While the larger size regime can be well described by line shapes calculated for clusters consisting of hundreds of molecules, the smaller size regime corresponds to methanol oligomers, predominantly of cyclic structure. There is little contribution from dimers to the spectra.
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| 10. |
- Björneholm, Olle, et al.
(författare)
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Deeper Insight into Depth-Profiling of Aqueous Solutions Using Photoelectron Spectroscopy
- 2014
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Ingår i: Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 118:50, s. 29333-29339
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Tidskriftsartikel (refereegranskat)abstract
- X-ray photoelectron spectroscopy (XPS) is widely used to probe properties such as molecular stoichiometry, microscopic distributions relative to the surface by so-called depth-profiling, and molecular orientation. Such studies usually rely on the core-level photoionization cross sections being independent of molecular composition. The validity of this assumption has recently been questioned, as a number of gas-phase molecules have been shown to exhibit photon-energy-dependent nonstochiometric intensity oscillations arising from EXAFS-like modulations of the photoionization cross section. We have studied this phenomenon in trichloroethanol in both gas phase and dissolved in water. The gas-phase species exhibits pronounced intensity oscillations, similar to the ones observed for other gas-phase molecules. These oscillations are also observed for the dissolved species, implying that the effect has to be taken into account when performing depth-profiling experiments of solutions and other condensed matter systems. The similarity between the intensity oscillations for gas phase and dissolved species allows us to determine the photoelectron kinetic energy of maximum surface sensitivity, approximate to 100 eV, which lies in the range of pronounced intensity oscillations.
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| 11. |
- Björneholm, Olle, et al.
(författare)
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Free clusters studied by core-level spectroscopies
- 2009
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Ingår i: Nuclear Instruments and Methods in Physics Research Section A. - : Elsevier BV. - 0168-9002 .- 1872-9576 .- 0167-5087. ; 601:1-2, s. 161-181
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Forskningsöversikt (refereegranskat)abstract
- In this review we describe the development and current status of free clusters studied using core-level spectroscopies. This topic ranges from simple model systems, such as rare gas clusters, to molecular clusters, and clusters of solids, held together by ionic, covalent and metallic bonding.
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| 12. |
- Björneholm, Olle, et al.
(författare)
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Superficial Tale of Two Functional Groups : On the Surface Propensity of Aqueous Carboxylic Acids, Alkyl Amines, and Amino Acids
- 2022
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Ingår i: Accounts of Chemical Research. - : American Chemical Society (ACS). - 0001-4842 .- 1520-4898. ; 55:23, s. 3285-3293
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Tidskriftsartikel (refereegranskat)abstract
- ConspectusThe gas-liquid interface of water is environmentally relevant due to the abundance of aqueous aerosol particles in the atmosphere. Aqueous aerosols often contain a significant fraction of organics. As aerosol particles are small, surface effects are substantial but not yet well understood. One starting point for studying the surface of aerosols is to investigate the surface of aqueous solutions. We review here studies of the surface composition of aqueous solutions using liquid-jet photoelectron spectroscopy in combination with theoretical simulations. Our focus is on model systems containing two functional groups, the carboxylic group and the amine group, which are both common in atmospheric organics. For alkanoic carboxylic acids and alkyl amines, we find that the surface propensity of such amphiphiles can be considered to be a balance between the hydrophilic interactions of the functional group and the hydrophobic interactions of the alkyl chain. For the same chain length, the neutral alkyl amine has a lower surface propensity than the neutral alkanoic carboxylic acid, whereas the surface propensity of the corresponding alkyl ammonium ion is higher than that of the alkanoic carboxylate ion. This different propensity leads to a pH-dependent surface composition which differs from the bulk, with the neutral forms having a much higher surface propensity than the charged ones. In aerosols, alkanoic carboxylic acids and alkyl amines are often found together. For such mixed systems, we find that the oppositely charged molecular ions form ion pairs at the surface. This cooperative behavior leads to a more organic-rich and hydrophobic surface than would be expected in a wide, environmentally relevant pH range. Amino acids contain a carboxylic and an amine group, and amino acids of biological origin are found in aerosols. Depending on the side group, we observe surface propensity ranging from surface-depleted to enriched by a factor of 10. Cysteine contains one more titratable group, which makes it exhibit more complex behavior, with some protonation states found only at the surface and not in the bulk. Moreover, the presence of molecular ions at the surface is seen to affect the distribution of inorganic ions. As the charge of the molecular ions changes with protonation, the effects on the inorganic ions also exhibit a pH dependence. Our results show that for these systems the surface composition differs from the bulk and changes with pH and that the results obtained for single-component solutions may be modified by ion-ion interactions in the case of mixed solutions.
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| 13. |
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| 14. |
- Carravetta, Vincenzo, et al.
(författare)
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An atomistic explanation of the ethanol-water azeotrope
- 2022
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 24:42, s. 26037-26045
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Tidskriftsartikel (refereegranskat)abstract
- Ethanol and water form an azeotropic mixture at an ethanol molecular percentage of similar to 91% (similar to 96% by volume), which prohibits ethanol from being further purified via distillation. Aqueous solutions at different concentrations in ethanol have been studied both experimentally and theoretically. We performed cylindrical micro-jet photoelectron spectroscopy, excited by synchrotron radiation, 70 eV above C1s ionization threshold, providing optimal atomic-scale surface-probing. Large model systems have been employed to simulate, by molecular dynamics, slabs of the aqueous solutions and obtain an atomistic description of both bulk and surface regions. We show how the azeotropic behaviour results from an unexpected concentration-dependence of the surface composition. While ethanol strongly dominates the surface and water is almost completely depleted from the surface for most mixing ratios, the different intermolecular bonding patterns of the two components cause water to penetrate to the surface region at high ethanol concentrations. The addition of surface water increases its relative vapour pressure, giving rise to the azeotropic behaviour.
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| 15. |
- Céolin, Denis, et al.
(författare)
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A rotatable electron spectrometer for multicoincidence experiments
- 2010
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Ingår i: Review of Scientific Instruments. - : AIP Publishing. - 1089-7623 .- 0034-6748. ; 81:6
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Tidskriftsartikel (refereegranskat)abstract
- We have developed a rotatable hemispherical spectrometer with good energy and angular resolution, which can be positioned with the lens axis arbitrarily within a solid angle of 1 pi. The collection angle of the emitted electrons with respect to the polarization axis of the light is set by means of a three-axes goniometer, operating under vacuum. An important requirement for this setup was the possibility to perform coincidences between the electron analyzed by the spectrometer and one or several other particles, such as ions, electrons, or photons. The lens system and the hemispheres have been designed to accommodate such experimental demands, regarding parameters such as the resolving power, the acceptance angle, or the width of the kinetic energy window which can be recorded for a given pass energy. We have chosen to detect the impact position of the electron at the focal plane of the hemispherical analyzer with a delay line detector and a time-to-digital converter as acquisition card rather than using a conventional charge-coupled device camera. (C) 2010 American Institute of Physics. [doi: 10.1063/1.3449333]
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| 16. |
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| 17. |
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| 18. |
- Ekholm, Victor, et al.
(författare)
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Anomalous surface behavior of hydrated guanidinium ions due to ion pairing
- 2018
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Ingår i: Journal of Chemical Physics. - : AIP Publishing. - 0021-9606 .- 1089-7690. ; 148:14
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Tidskriftsartikel (refereegranskat)abstract
- Surface affinity of aqueous guanidinium chloride (GdmCl) is compared to that of aqueous tetrapropylammonium chloride (TPACl) upon addition of sodium chloride (NaCl) or disodium sulfate (Na2SO4). The experimental results have been acquired using the surface sensitive technique X-ray photoelectron spectroscopy on a liquid jet. Molecular dynamics simulations have been used to produce radial distribution functions and surface density plots. The surface affinities of both TPA(+) and Gdm(+) increase upon adding NaCl to the solution. With the addition of Na2SO4, the surface affinity of TPA(+) increases, while that of Gdm(+) decreases. From the results of MD simulations it is seen that Gdm(+) and SO42- ions form pairs. This finding can be used to explain the decreased surface affinity of Gdm(+) when co-dissolved with SO42- ions. Since SO42- ions avoid the surface due to the double charge and strong water interaction, the Gdm(+)-SO42- ion pair resides deeper in the solutions' bulk than the Gdm(+) ions. Since TPA(+) does not form ion pairs with SO42-, the TPA(+) ions are instead enriched at the surface.
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| 19. |
- Ekholm, Victor, 1989-, et al.
(författare)
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Strong enrichment of atmospherically relevant organic ions at the aqueous interface : the role of ion pairing and cooperative effects
- 2018
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : ROYAL SOC CHEMISTRY. - 1463-9076 .- 1463-9084. ; 20:42, s. 27185-27191
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Tidskriftsartikel (refereegranskat)abstract
- Surface affinity, orientation and ion pairing are investigated in mixed and single solute systems of aqueous sodium hexanoate and hexylammonium chloride. The surface sensitive X-ray photoelectron spectroscopy technique has been used to acquire the experimental results, while the computational data have been calculated using molecular dynamics simulations. By comparing the single solute solutions with the mixed one, we observe a non-linear surface enrichment and reorientation of the organic ions with their alkyl chains pointing out of the aqueous surface. We ascribe this effect to ion paring between the charged functional groups on the respective organic ion and hydrophobic expulsion of the alkyl chains from the surface in combination with van der Waals interactions between the alkyl chains. These cooperative effects lead to a substantial surface enrichment of organic ions, with consequences for aerosol surface properties.
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| 20. |
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| 21. |
- Eriksson, Susanna K., et al.
(författare)
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Solvent Dependence of the Electronic Structure of I- and I-3(-)
- 2014
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Ingår i: Journal of Physical Chemistry B. - : American Chemical Society (ACS). - 1520-6106 .- 1520-5207. ; 118:11, s. 3164-3174
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Tidskriftsartikel (refereegranskat)abstract
- We present synchrotron-based I4d photoelectron spectroscopy experiments of solutions from LiI and LiI3 in water, ethanol, and acetonitrile. The experimentally determined solvent-induced binding energy shifts (SIBES) for the monatomic I- anion are compared to predictions from simple Born theory, PCM calculations, as well as multiconfigurational quantum chemical spectral calculations from geometries obtained through molecular dynamics of solvated clusters. We show that the SIBES for I- explicitly depend on the details of the hydrogen bonding configurations of the solvent to the I- and that static continuum models such as the Born model cannot capture the trends in the SIBES observed both in experiments and in higher-level calculations. To extend the discussion to more complex polyatomic anions, we also performed experiments on I-3(-) and I-/I-3(-) mixtures in different solvents and the results are analyzed in the perspective of SIBES. The experimental SIBES values indicate that the solvation effects even for such similar anions as I- and I-3(-) can be rather different in nature.
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| 22. |
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| 23. |
- Feifel, Raimund, et al.
(författare)
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From localised to delocalised electronic states in free Ar, Kr and Xe clusters
- 2004
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Ingår i: European Physical Journal D. Atomic, Molecular, Optical and Plasma Physics. - : Springer Science and Business Media LLC. - 1434-6060 .- 1434-6079. ; 30:3, s. 343-351
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Tidskriftsartikel (refereegranskat)abstract
- We present new results for the inner valence levels of clusters of the three inert gases Ar, Kr and Xe based on photoelectron spectroscopy studies. The inner valence levels are compared to the localised core levels and to the delocalised outer valence levels. This comparison shows a gradual change from a relatively localised behaviour for Ar inner valence 3s, over the intermediate case of Kr inner valence 4s, to a more delocalised behaviour for Xe inner valence 5s. This change correlates well with the ratio between the orbital sizes and the interatomic distances. The Kr4s intermediate case is found to exhibit characteristics of both localised and delocalised behaviour.
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| 24. |
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| 25. |
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| 26. |
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| 27. |
- Foerstel, Marko, et al.
(författare)
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Observation of electronic energy bands in argon clusters
- 2010
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Ingår i: Physical Review B. Condensed Matter and Materials Physics. - 1098-0121 .- 1550-235X. ; 82:12, s. 125450-
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Tidskriftsartikel (refereegranskat)abstract
- The 3p valence region of argon clusters has been investigated with photoemission near the photoionization threshold. A strong feature between 14.6 and 15.3 eV binding energy shows a photon-energy dependence indicative of electronic-energy band dispersion. A similar feature at approximately the same binding energy and with a similar dispersion occurs in photoemission spectra of both the ordered and disordered solids. The effect is already fully developed for scaling-law mean cluster sizes < N > of approximately 200 atoms, thus showing an early onset of bulklike electronic properties.
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| 28. |
- Förstel, Marko, et al.
(författare)
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Energy band dispersion in photoemission spectra of argon clusters
- 2011
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Ingår i: Journal of Electron Spectroscopy and Related Phenomena. - : Elsevier BV. - 0368-2048 .- 1873-2526. ; 184:3-6, s. 107-112
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Tidskriftsartikel (refereegranskat)abstract
- Using photoemission we have investigated free argon clusters from a supersonic nozzle expansion in the photon energy range from threshold up to 28 eV. Measurements were performed both at high resolution with a hemispherical electrostatic energy analyser and at lower resolution with a magnetic bottle device. The latter experiments were performed for various mean cluster sizes. In addition to the approximate to 15eV broad 3p-derived valence band seen in previous work, there is a sharper feature at approximate to 15eV binding energy. Surprisingly for non-oriented clusters, this peak shifts smoothly in binding energy over the narrow photon energy range 15.5-17.7 eV, indicating energy band dispersion. The onset of this bulk band-like behaviour could be determined from the cluster size dependence.
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| 29. |
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| 30. |
- Gopakumar, Geethanjali, et al.
(författare)
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Probing aqueous ions with non-local Auger relaxation
- 2022
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Ingår i: Physical Chemistry Chemical Physics. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 24:15, s. 8661-8671
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Tidskriftsartikel (refereegranskat)abstract
- Non-local analogues of Auger decay are increasingly recognized as important relaxation processes in the condensed phase. Here, we explore non-local autoionization, specifically Intermolecular Coulombic Decay (ICD), of a series of aqueous-phase isoelectronic cations following 1s core-level ionization. In particular, we focus on Na+, Mg2+, and Al3+ ions. We unambiguously identify the ICD contribution to the K-edge Auger spectrum. The different strength of the ion-water interactions is manifested by varying intensities of the respective signals: the ICD signal intensity is greatest for the Al3+ case, weaker for Mg2+, and absent for weakly-solvent-bound Na+. With the assistance of ab initio calculations and molecular dynamics simulations, we provide a microscopic understanding of the non-local decay processes. We assign the ICD signals to decay processes ending in two-hole states, delocalized between the central ion and neighbouring water. Importantly, these processes are shown to be highly selective with respect to the promoted water solvent ionization channels. Furthermore, using a core-hole-clock analysis, the associated ICD timescales are estimated to be around 76 fs for Mg2+ and 34 fs for Al3+. Building on these results, we argue that Auger and ICD spectroscopy represents a unique tool for the exploration of intra- and inter-molecular structure in the liquid phase, simultaneously providing both structural and electronic information.
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| 31. |
- Gopakumar, Geethanjali, 1992-, et al.
(författare)
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The Surface Composition of Amino Acid - Halide Salt Solutions is pH-Dependent
- 2022
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Ingår i: Environmental Science: Atmospheres. ; :3
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Tidskriftsartikel (refereegranskat)abstract
- In atmospheric aerosol particles, the chemical surface composition governs both heterogeneous chemical reactions with gas-phase species and the ability to act as nuclei for cloud droplets. The pH in aerosol droplets is expected to affect these properties, but it is very challenging to measure the pH in individual droplets, precluding the investigation of its influence on the particle's surface composition. In this work, we use photoelectron spectroscopy to explore how the surface composition of aqueous solutions containing inorganic salt and amino acids changes as a function of pH. We observe a change by a factor of 4-5 of the relative distribution of inorganic ions at the surface of a liquid water jet, as a function of solution pH and type of amino acid in the solution. The driving forces for the surface enhancement or depletion are ion pairing and the formation of charged layers close to the aqueous surface. Our findings apply to any aqueous interface at which organic species with charged functional groups are present.
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| 32. |
- Gopakumar, Geethanjali, et al.
(författare)
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The surface composition of amino acid - halide salt solutions is pH-dependent
- 2022
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Ingår i: Environmental Science: Atmospheres. - : Royal Society of Chemistry (RSC). - 2634-3606. ; 2:3, s. 441-448
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Tidskriftsartikel (refereegranskat)abstract
- In atmospheric aerosol particles, the chemical surface composition governs both heterogenous chemical reactions with gas-phase species and the ability to act as nuclei for cloud droplets. The pH in aerosol particles is expected to affect these properties, but it is very challenging to measure the pH in individual droplets, precluding the investigation of its influence on the particle's surface composition. In this work, we use photoelectron spectroscopy to explore how the surface composition of aqueous solutions containing inorganic salt and amino acids changes as a function of pH. We observe a change by a factor of 4-5 of the relative distribution of inorganic ions at the surface of a liquid water jet, as a function of solution pH and type of amino acid in the solution. The driving forces for the surface enhancement or depletion are ion pairing and the formation of charged layers close to the aqueous surface.
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| 33. |
- Hergenhahn, Uwe, et al.
(författare)
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3p valence photoelectron spectrum of Ar clusters
- 2009
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Ingår i: Physical Review B. Condensed Matter and Materials Physics. - 1098-0121 .- 1550-235X. ; 79:15, s. 155448-
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Tidskriftsartikel (refereegranskat)abstract
- The shape of the outer valence (3p) photoelectron spectrum of Ar clusters is investigated by vacuum ultraviolet photoionization with synchrotron radiation. We show the dependence of the spectrum on cluster size and the change in its shape with photon energy. Inelastic losses due to intracluster photoelectron scattering are most important for changes in the photoelectron main line and explain the appearance of additional peaks. A comparison of our results to earlier work on bulk condensed Ar and Ar thin films is given. Evidence for a deviation of the photoionization cross sections for clusters from the atomic ones has not been found.
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| 34. |
- Holland, D. M. P., et al.
(författare)
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A study of the photoionisation dynamics of chloromethane and iodomethane
- 2006
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Ingår i: Chemical Physics. - : Elsevier BV. - 0301-0104. ; 326, s. 535-550
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Tidskriftsartikel (refereegranskat)abstract
- Angle resolved valence shell photoelectron spectra of chloromethane and iodomethane have been recorded using synchrotron radiation in the photon energy range 14–120 eV. These have allowed photoelectron angular distributions and branching ratios to be determined not only for the main bands associated with the single-hole states but also for the satellite structure due to many-electron effects. The continuum multiple scattering approach has been used to calculate photoelectron asymmetry parameters and branching ratios for the valence orbitals of CH3Cl and CH3I, and also for the I 4d subshell. A comparison between the experimental data and the theoretical predictions has enabled the influence of Cooper minima, shape resonances and intershell coupling to be assessed. The asymmetry parameters and branching ratio for the spin–orbit split components of the CH3I+ X~2E state have been measured and exhibit a spectral behaviour almost identical to that of the corresponding data for the Xe 5p3/2 and 5p1/2 levels. The many-body Green’s function approach has been employed to evaluate the ionisation energies and spectral intensities of all valence states and the results have facilitated an interpretation of the satellite structure. The I 4d shake-up, shake-off and Auger spectra of iodomethane have been recorded and many of the Auger peaks have been assigned using previously determined ionisation energies of doubly charged valence states.
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| 35. |
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| 36. |
- Josefsson, Ida, et al.
(författare)
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Collective hydrogen-bond dynamics dictates the electronic structure of aqueous I-3(-)
- 2013
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Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 15:46, s. 20189-20196
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Tidskriftsartikel (refereegranskat)abstract
- The molecular and electronic structures of aqueous I-3 and I ions have been investigated through ab initio molecular dynamics (MD) simulations and photoelectron (PE) spectroscopy of the iodine 4d core levels. Against the background of the theoretical simulations, data from our I4d PE measurements are shown to contain evidence of coupled solute-solvent dynamics. The MD simulations reveal large amplitude fluctuations in the I-I distances, which couple to the collective rearrangement of the hydrogen bonding network around the I-3(-) ion. Due to the high polarizability of the I-3(-) ion, the asymmetric I-I vibration reaches partially dissociated configurations, for which the electronic structure resembles that of I-2 + I-. The charge localization in the I-3(-) ion is found to be moderated by hydrogen-bonding. As seen in the PE spectrum, these soft molecular vibrations are important for the electronic properties of the I-3(-) ion in solution and may play an important role in its electrochemical function.
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| 37. |
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| 38. |
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| 39. |
- Kowalik, Iwona, et al.
(författare)
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Description of the new I1011 beamline for magnetic measurements using synchrotron radiation at MAX-lab
- 2010
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Ingår i: Journal of Physics, Conference Series. - : IOP Science. - 1742-6588 .- 1742-6596. ; 211:1, s. 012030-
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Tidskriftsartikel (refereegranskat)abstract
- We report on the characterization of the new I1011 beamline at the MAX-II storage ring, in the MAX-lab synchrotron radiation laboratory and give examples of first results. This beamline is using an Elliptically Polarizing Undulator source, producing soft x-rays of a variable polarization state. It delivers high flux and high brightness circularly polarized x-rays in the energy range 0.2 to 1.7 keV, covering the L-edges of the late 3d elements. The new beamline will operate with an octupole magnet endstation. It is specially engineered to solve the problem of the limited optical access typically associated with magnetic fields and synchrotron radiation endstations. Eight water-cooled magnets allow the application of the magnetic field of up to 1 T in any direction. X-ray absorption spectroscopy, X-ray resonant reflectivity and the corresponding magnetic variants, i.e., XMCD, XMLD and XRMS experiments are possible also under an applied magnetic field. The high flux allows working with dilute magnetic systems such as ultra-thin films and nano structures.
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| 40. |
- Lindblad, Andreas, 1978-
(författare)
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A Treatise on the Geometric and Electronic Structure of Clusters : Investigated by Synchrotron Radiation Based Electron Spectroscopies
- 2008
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Clusters are finite ensembles of atoms or molecules with sizes in the nanometer regime (i.e. nanoparticles). This thesis present results on the geometric and electronic structure of homogeneous and heterogeneous combinations of atoms and molecules. The systems have been studied with synchrotron radiation and valence, core and Auger electron spectroscopic techniques.The first theme of the thesis is that of mixed clusters. It is shown that by varying the cluster production technique both structures that are close to that predicted by equilibrium considerations can be attained as well as far from equilibrium structures.Electronic processes following ionization constitute the second theme. The post-collision interaction phenomenon, energy exchange between the photo- and the Auger electrons, is shown to be different in clusters of argon, krypton and xenon. A model is proposed that takes polarization screening in the final state into account. This result is of general character and should be applicable to the analysis of core level photoelectron and Auger electron spectra of insulating and semi-conducting bulk materials as well.Interatomic Coloumbic Decay is a process that can occur in the condensed phases of weakly bonded systems. Results on the time-scale of the process in Ne clusters and mixed Ar/Ne clusters are herein discussed, as well observations of resonant contributions to the process. In analogy to Auger vis-à-vis Resonant Auger it is found that to the ICD process there is a corresponding Resonant ICD process possible. This has later been observed in other systems and by theoretical calculations as well in subsequent works by other groups.Delocalization of dicationic valence final states in the hydrogen bonded ammonia clusters and aqueous ammonia has also been investigated by Auger electron spectroscopy. With those results it was possible to assign a previously observed feature in the Auger electron spectrum of solid ammonia.
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| 41. |
- Lindblad, Andreas, et al.
(författare)
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Chemical shifts of small heterogeneous Ar/Xe clusters
- 2011
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Ingår i: Physical Review B. Condensed Matter and Materials Physics. - 1098-0121 .- 1550-235X. ; 83:12, s. 125414-
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Tidskriftsartikel (refereegranskat)abstract
- Heterogeneous rare-gas clusters produced by a coexpansion of an argon/xenon mixture have been studied using synchrotron-radiation-based photoelectron spectroscopy. Both valence and Xe 4d(5/2) core-level photoelectron spectra were recorded for three different concentrations of the primary argon/xenon mixture and, for those mixtures, spectra were recorded at several different stagnation conditions. The studied size regime of the mixed clusters ranges from large, similar to those studied in an earlier paper [Phys. Rev. A 69, 031210(R) (2004)], to very small-as reflected in the cluster line shapes and chemical shifts. The chemical shifts obtained from a curve fitting procedure similar to that used in our earlier paper are discussed in terms of the mixed cluster structure which can be expected from equilibrium considerations and the Lennard-Jones parameters of the constituent atoms. Molecular dynamics simulations of the vertical polarization shifts allow more specific assignments of "on-top" sites and interfacial sites.
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| 42. |
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| 43. |
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| 44. |
- Lindblad, A, et al.
(författare)
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The geometric structure of pure SF6 and mixed Ar/SF6 clusters investigated by core level photoelectron spectroscopy
- 2009
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Ingår i: Surface Science. - : Elsevier BV. - 0039-6028 .- 1879-2758. ; 603:3, s. 433-436
-
Tidskriftsartikel (refereegranskat)abstract
- The S 2p core level photoelectron spectra of Sulphurhexafluoride Clusters have been investigated together with heterogeneous Ar/SF6 clusters, created by doping Ar host clusters (with a mean size of 3600 atoms) with the molecule. Surface and bulk features are resolved both in the argon 2p and the sulphur 2p core level photoelectron spectra. For the latter level such features were only observed in the pure cluster case; a single feature characterizes the S 2p core level spectra of SF6 doped argon clusters. From the chemical shifts, investigated with respect to SF6 doping pressure. It can be concluded that the host clusters get smaller with increasing doping pressures and that the SF6 molecules predominantly stay below the cluster surface, whereas the Argon core stays intact. We have neither observed features corresponding to SF6 on the cluster Surface, nor features corresponding to molecules deep inside the bulk in any of the spectra from the pick-up experiments.
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| 45. |
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| 46. |
- Lundwall, M., et al.
(författare)
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Neighbor-induced photoelectron recapture in argon clusters : A photon-energy-dependent study of Auger spectra
- 2008
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Ingår i: Physical Review A. Atomic, Molecular, and Optical Physics. - 1050-2947 .- 1094-1622. ; 78:6, s. 065201-
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Tidskriftsartikel (refereegranskat)abstract
- A photon-energy-dependent experimental study of the L2,3M2,3M2,3 Auger transitions in argon clusters is presented, and features without atomic counterparts are observed in the spectra up to photon energies at least 30 eV above the L2,3 threshold. We propose that these features are due to the process of neighbor-induced recapture, in which the outgoing photoelectron is backscattered by neighboring atoms in the cluster, loses energy in a Bremsstrahlung-like inverse photoemission process, and is recaptured in a Rydberg orbital of the core-ionized atom before Auger decay.
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| 47. |
- Lundwall, Marcus, et al.
(författare)
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Photon energy dependent intensity variations observed in Auger spectra of free argon clusters
- 2006
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Ingår i: Journal of Physics B: Atomic, Molecular and Optical Physics. - : IOP Publishing. - 0953-4075 .- 1361-6455. ; 39:16, s. 3321-3333
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Tidskriftsartikel (refereegranskat)abstract
- Photon energy dependent intensity variations are experimentally observed in the L2,3M2,3M2,3 Auger spectra of argon clusters. Two cluster sizes are examined in the present study. Extrinsic scattering effects, both elastic and inelastic, involving the photoelectron are discussed and suggested as the explanation of the variations in the Auger signal. The atoms in the first few coordination shells surrounding the core-ionized atom are proposed to be the main targets for the scattering processes.
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| 48. |
- Lundwall, Marcus, et al.
(författare)
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Preferential site occupancy observed in coexpanded argon-krypton clusters
- 2006
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Ingår i: Physical Review A. Atomic, Molecular, and Optical Physics. - 1050-2947 .- 1094-1622. ; 74:4, s. 043206-
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Tidskriftsartikel (refereegranskat)abstract
- Free heterogeneous argon-krypton clusters have been produced by coexpansion and investigated by means of x-ray photoelectron spectroscopy. By examining cluster surface and bulk binding energy shifts, relative intensities, and peak widths, we show that in the mixed argon-krypton clusters the krypton atoms favor the bulk and argon atoms are pushed to the surface. Furthermore, we show that krypton atoms in the surface layer occupy high-coordination sites and that heterogeneous argon-krypton clusters produced by coexpansion show the same surface structure as argon host clusters doped with krypton. These observations are supported by site-dependent calculations of chemical shifts.
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| 49. |
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| 50. |
- Lundwall, Marcus, 1977-
(författare)
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Rare-gas Clusters Studied by Electron Spectroscopy : Structure of Heterogeneous Clusters and Effects of Electron Scattering on Auger Decay
- 2007
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- In this Thesis experimental studies of nano-clusters using synchrotron radiation based photoelectron (UPS and XPS) and Auger Electron Spectroscopy (AES) are presented. The investigations may be divided into two parts where the first reports on the structure of heterogeneous two component clusters, and the second concerns electronic decay processes.Using photoelectron spectroscopies as investigative tools the radial composition of heteroclusters of argon mixed with xenon, krypton or neon has been determined. Two methods of heterogeneous cluster production were employed: co-expansion and doping/pick-up. By analyzing the line shapes, energy positions, and widths of the spectral cluster features the radial composition of the clusters produced by co-expansion were found to form close-to-equilibrium structures, placing the component with larger cohesive energy in the cluster core while the second component was to varying degree segregated toward the surface. By instead using the doping/pick-up technique the opposite radial structures, i.e. far-from-equilibrium structures, may be formed. In the case of argon/krypton clusters a similar surface structure is formed regardless of production technique.The second part of the Thesis concerns post-ionization decay processes. Experimental evidence for the Interatomic Coulombic Decay process, a theoretically predicted decay channel, is presented in a study of homogeneous neon clusters. The time scale of the decay was determined to 6±1 fs for bulk atoms and >30 fs for surface atoms in the neon cluster, showing the connection between local geometry and dynamics of the decay.Another channel for electronic relaxation is Auger decay. This Thesis presents a method of disentangling the spectral surface and bulk responses from clusters in Auger spectra. Studies of argon clusters show that the AES technique is more surface sensitive than XPS, even at the same electron kinetic energy. Furthermore, the effect scattering of the photoelectron has on the Auger spectra was investigated. Special effort was put into explaining an experimentally observed photon energy dependent intensity appearing on the high-kinetic energy side on the Auger signal. We propose that this intensity is due to a solid state-specific photoelectron recapture process we name Pre-Auger Recapture (PAR), which affects the kinetic energy of the Auger electrons.
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