| 1. |
- Söderström, Johan, et al.
(författare)
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Functionalized nanoparticles in aqueous surroundings probed by X-ray photoelectron spectroscopy
- 2011
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Ingår i: Journal of Electron Spectroscopy and Related Phenomena. - : Elsevier BV. - 0368-2048 .- 1873-2526. ; 184:7, s. 375-378
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Tidskriftsartikel (refereegranskat)abstract
- In this paper we present the first core-level photoelectron spectroscopic study of solid nanoparticles in liquid water. The particles are SiO(2)-based with an average diameter of 70 nm and functionalized with carboxylic groups. Despite that the sample is very dilute, we show that it is possible to obtain reasonable photoemission signal containing chemical information about both the ligands and the outermost parts of the SiO(2)-based core of the nanoparticles. We argue that this is due to a significant enrichment of the dispersed particles at the liquid/vapor interface. This proof-of-principle study expands the field of X-ray photoelectron spectroscopy by adding a new, wide and important class of systems that can be studied.
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| 2. |
- Abid, Abdul Rahman, et al.
(författare)
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Forming Bonds While Breaking Old Ones : Isomer-Dependent Formation of H3O+ from Aminobenzoic Acid During X-ray-Induced Fragmentation
- 2023
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Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 127:6, s. 1395-1401
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Tidskriftsartikel (refereegranskat)abstract
- Intramolecular hydrogen transfer, a reaction where donor and acceptor sites of a hydrogen atom are part of the same molecule, is a ubiquitous reaction in biochemistry and organic synthesis. In this work, we report hydronium ion (H3O+) production from aminobenzoic acid (ABA) after core-level ionization with soft X-ray synchrotron radiation. The formation of H3O+ during the fragmentation requires that at least two hydrogen atoms migrate to one of the oxygen atoms within the molecule. The comparison of two structural isomers, ortho- and meta-ABA, revealed that the production of H3O+ depends strongly on the structure of the molecule, the ortho-isomer being much more prone to produce H3O+. The isomer-dependency suggests that the amine group acts as a donor in the hydrogen transfer process. In the case of ortho-ABA, detailed H3O+ production pathways were investigated using photoelectron-photoion-photoion coincidence (PEPIPICO) spectroscopy. It was found that H3O+ can result from a direct two-body dissociation but also from sequential fragmentation processes.
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| 3. |
- Abid, Abdul Rahman, et al.
(författare)
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The effect of relative humidity on CaCl2 nanoparticles studied by soft X-ray absorption spectroscopy
- 2021
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Ingår i: RSC Advances. - : Royal Society of Chemistry. - 2046-2069. ; 11:4, s. 2103-2111
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Tidskriftsartikel (refereegranskat)abstract
- Ca- and Cl-containing nanoparticles are common in atmosphere, originating for example from desert dust and sea water. The properties and effects on atmospheric processes of these aerosol particles depend onthe relative humidity (RH) as they are often both hygroscopic and deliquescent. We present here a study of surface structure of free-flying CaCl2 nanoparticles (CaCl2-NPs) in the 100 nm size regime prepared at different humidity levels (RH: 11–85%). We also created mixed nanoparticles by aerosolizing a solution ofCaCl2 and phenylalanine (Phe), which is a hydrophobic amino acid present in atmosphere. Information of hydration state of CaCl2-NPs and production of mixed CaCl2 + Phe nanoparticles was obtained using soft X-ray absorption spectroscopy (XAS) at Ca 2p, Cl 2p, C 1s, and O 1s edges. We also report Ca 2p andCl 2p X-ray absorption spectra of an aqueous CaCl2 solution. The O 1s X-ray absorption spectra measured from hydrated CaCl2-NPs resemble liquid-like water spectrum, which is heavily influenced by the presence of ions. Core level spectra of Ca2+ and Cl- ions do not show a clear dependence of % RH, indicating that the first coordination shell remains similar in all measured hydrated CaCl2-NPs, but they differ from aqueous solution and solid CaCl2.
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| 4. |
- Abid, Abdul Rahman
(författare)
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X-ray Absorption and Fragmentationas Initial Steps of Radiation Damage in Free Organic Molecules and Nanoparticles
- 2021
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Understanding the molecular radiation damage is crucial in radiobiology, molecular physics, and atmospheric science. In this thesis, the initial steps of radiation damage of anhydrous gas-phase molecules and hydrated nanoparticles were studied using synchrotron radiation based electron-ion coincidence spectroscopy and X-ray absorption spectroscopy under vacuum conditions. Electron - ion coincidence spectroscopy was used to study the photofragmentation and molecular dynamics of the isolated gas-phase molecules. In addition to the photofragmentation of the gas-phase molecules, the effect of the initial ionization site, initial molecular geometry, and the intramolecular chemical environment has been studied. In avobenzone, core ionization leads to massive fragmentation, with a slight site-selectivity concerning fragment production. In ortho-aminobenzoic acid, core ionization leads to the production of a hydronium ion, indicating that the importance of functional group's position for double intramolecular hydrogen transfer. X-ray absorption spectroscopy was used to probe hydrated nanoparticles prepared at different relative humidities. In hydrated inorganic and mixed inorganic-organic nanoparticles, water is present in a liquid-like state. With different ranges of relative humidity, the primary hydration layers of the hydrated nanoparticles stays the same. In mixed nanoparticles, there is evidence for interaction between the included organic biomolecule with the inorganic and/or water molecules.
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| 5. |
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| 6. |
- Akiyama, Tomoko, et al.
(författare)
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Influence of Ionization on the Dynamics of Hydrocarbons
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- The structural changes of four hydrocarbons induced by ionization was investigated using molecular dynamics simulations based on density functional theory within the Born-Oppenheimer approximation. Bond lengths, bond breaking and proton rearrangement was analysed for propane, propene, propyne and propadiene at charges ranging from 0 to +3. Similar to the case of amino acids, the back-bone of linear hydrocarbons is stabilized by reducing theeffectiv elevel of ionization through dropping protons. Subsequent iniozations, up the the level of 3+, do not break thelinear carbon chain within 250 fs, however the bond-orderis reduced, and bond-distances approach that of a single-bond
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| 7. |
- Akiyama, Tomoko
(författare)
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Ionization Influence on the Dynamics of Simple Organic Molecules
- 2023
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Licentiatavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This licentiate thesis is devoted to the investigation of how bonding in simple organic molecules are affected by X-ray beam irradiation. The investigation targets molecules with three carbons as their main-chain structure. The stability of the bonds under ionization are simulated using the SIESTA package. SIESTA is a simulation package that provides molecular dynamics simulations based on density functional theory within the Born-Oppenheimer approximation. The aim of this study is to understand statistically the damaging process and selectivity among different types of bond. As the first targets, 4 hydrocarbons are investigated. They are propane, propene, propyne and propadiene, which have different combinations of single, double and triple bonds as their main-chain structures. Depending on the combinations, the structures can be either symmetric around the central atom or not. The structure of the symmetric molecules propane and propadiene are stable until charge +3. In contrast, the asymmetric molecules propene and propyne, the main-chain bonds show a tendency towards a more similar bond-distance as the level of ionization increases. In addition, hydrogens relocation occurs in propene, leading to a symmetric structure. Secondly, the bond fluctuations are investigated among 4 types of three-carbon molecules which have functional parts. Alcohol and carboxyl groups molecules show the stable bond integrities at charging 0 to +2. On the other hand, the carbon-carbon bonds in molecules with acetyl and ketone groups are broken by ionization. Comparing the 8 kinds of bond breaking processes in these molecules, this statistical study gives an insight to organic molecules bonding systems.
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| 8. |
- Andersson, T., et al.
(författare)
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Electronic structure transformation in small bare Au clusters as seen by x-ray photoelectron spectroscopy
- 2017
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Ingår i: Journal of Physics B. - : IOP Publishing. - 0953-4075 .- 1361-6455. ; 50:1
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Tidskriftsartikel (refereegranskat)abstract
- Free bare gold clusters in the size range from few tens to few hundred atoms (<= 1 nm dimensions) have been produced in a beam, and the size-dependent development of their full valence band including the 5d and 6s parts has been mapped 'on the fly' by synchrotron-based photoelectron spectroscopy. The Au 4f core level has been also probed, and the cluster-specific Au 4f ionization energies have been used to estimate the cluster size. The recorded in the present work valence spectra of the small clusters are compared with the spectra of the large clusters (N similar to 10(3)) created by us using a magnetron-based gas aggregation source. The comparison shows a substantially narrower 5d valence band and the decrease in its splitting for gold clusters in the size range of few hundred atoms and below. Our DFT calculations involving the pseudopotential method show that the 5d band width of the ground state increases with the cluster size and by the size N = 20 becomes comparable with the experimental width of the valence photoelectron spectrum. Similar to the earlier observations on supported clusters we interpret our experimental and theoretical results as due to the undercoordination of a large fraction of atoms in the clusters with N similar to 10(2) and below. The consequences of such electronic structure of small gold clusters are discussed in connection with their specific physical and chemical properties related to nanoplasmonics and nanocatalysis.
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| 9. |
- Andersson, Tomas, 1984-
(författare)
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Free Metal Clusters Studied by Photoelectron Spectroscopy
- 2012
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- Clusters are aggregates of a finite number of atoms or molecules. In the present work, free clusters out of metallic parent materials have been created and studied by synchrotron radiation-based photoelectron spectroscopy. The clusters have been formed and studied in a beam and the electronic structure of the clusters has been investigated. Conclusions have been drawn about the spatial distribution of atoms of different elements in bi-component clusters, about the development of metallicity in small clusters, and about the excitation of plasmons.Bi-component alloy clusters of sodium and potassium and of copper and silver have been produced. The site-sensitivity of the photoelectron spectroscopy technique has allowed us to probe the geometric distribution of the atoms of the constituent elements by comparing the responses from the bulk and surface of the clusters. In both cases, we have found evidence for a surface-segregated structure, with the element with the largest atoms and lowest cohesive energy (potassium and silver, correspondingly) dominating the surface and with a mixed bulk.Small clusters of tin and lead have been probed to investigate the development of metallicity. The difference in screening efficiency between metals and non-metals has been utilized to determine in what size range an aggregate of atoms of these metallic parent materials stops to be metallic. For tin this has been found to occur below ~40 atoms while for lead it happened somewhere below 20-30 atoms.The excitation of bulk and surface plasmons has been studied in clusters of sodium, potassium, magnesium and aluminium, with radii in the nanometer range. The excitation energies have been found to be close to those of the corresponding macroscopic solids. We have also observed spectral features corresponding to multi-quantum plasmon excitation in clusters of Na and K. Such features have in macroscopic solids been interpreted as due to harmonic plasmon excitation. Our observations of features corresponding to the excitation of one bulk and one surface plasmon however suggest the presence of sequential excitation in clusters.
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| 10. |
- 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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