| 1. |
- Abid, Abdul Rahman, et al.
(författare)
-
Electron-ion coincidence spectroscopy of a large organic molecule : photofragmentation of avobenzone after valence and core ionisation
- 2020
-
Ingår i: Journal of Physics B: Atomic, Molecular and Optical Physics. - : IOP Publishing. - 0953-4075 .- 1361-6455. ; 53:24
-
Tidskriftsartikel (refereegranskat)abstract
- The Avobenzone (AVOB) molecule is very photoactive and undergoes irreversible degradation upon irradiation. We studied its valence and core-level (C1s and O1s) photoionisation and subsequent photofragmentation with photoelectron spectroscopy and photoelectron-photoion-photoion coincidence (PEPIPICO) spectroscopy. AVOB is one of the largest molecules studied with this technique. The results show that the AVOB molecule dissociates into an extensive range of fragments by different pathways with little element or site-selectivity. The coincident maps were used to determine selected fragment separation sequences by analysing the slopes of patterns from ion pairs after the core ionisation. Charge delocalisation over the benzene rings and their relative stability favor fragmentation by cleavage of the bridge between them.
|
|
| 2. |
- Abid, Abdul Rahman, et al.
(författare)
-
Forming Bonds While Breaking Old Ones : Isomer-Dependent Formation of H3O+ from Aminobenzoic Acid During X-ray-Induced Fragmentation
- 2023
-
Ingår i: Journal of Physical Chemistry A. - : American Chemical Society (ACS). - 1089-5639 .- 1520-5215. ; 127:6, s. 1395-1401
-
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.
|
|
| 3. |
- Abid, Abdul Rahman, et al.
(författare)
-
The effect of relative humidity on CaCl2 nanoparticles studied by soft X-ray absorption spectroscopy
- 2021
-
Ingår i: RSC Advances. - : Royal Society of Chemistry. - 2046-2069. ; 11:4, s. 2103-2111
-
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.
|
|
| 4. |
- Abid, Abdul Rahman
(författare)
-
X-ray Absorption and Fragmentationas Initial Steps of Radiation Damage in Free Organic Molecules and Nanoparticles
- 2021
-
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.
|
|
| 5. |
- Akiyama, Tomoko
(författare)
-
Ionization Influence on the Dynamics of Simple Organic Molecules
- 2023
-
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.
|
|
| 6. |
- Björneholm, Olle, et al.
(författare)
-
Hot spots of radiation damage from extensive water ionization around metal ions
- 2023
-
Ingår i: Nature Chemistry. - : Springer Nature. - 1755-4330 .- 1755-4349. ; 15:10, s. 1338-1339
-
Tidskriftsartikel (övrigt vetenskapligt/konstnärligt)abstract
- Radiation damage in biological systems by radicals and low-energy electrons formed from water ionization is a consequence of ultrafast processes that follow core-level ionization of hydrated metal ions. More details of the complex pathway are now revealed from the study of aluminium-ion relaxation through sequential electron-transfer-mediated decay.
|
|
| 7. |
- Björneholm, Olle, et al.
(författare)
-
Superficial Tale of Two Functional Groups : On the Surface Propensity of Aqueous Carboxylic Acids, Alkyl Amines, and Amino Acids
- 2022
-
Ingår i: Accounts of Chemical Research. - : American Chemical Society (ACS). - 0001-4842 .- 1520-4898. ; 55:23, s. 3285-3293
-
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.
|
|
| 8. |
- Bloß, Dana, et al.
(författare)
-
X-ray radiation damage cycle of solvated inorganic ions
- 2024
-
Ingår i: Nature Communications. - : Springer Nature. - 2041-1723. ; 15:1
-
Tidskriftsartikel (refereegranskat)abstract
- X-ray-induced damage is one of the key topics in radiation chemistry. Substantial damage is attributed to low-energy electrons and radicals emerging from direct inner-shell photoionization or produced by subsequent processes. We apply multi-electron coincidence spectroscopy to X-ray-irradiated aqueous solutions of inorganic ions to investigate the production of low-energy electrons (LEEs) in a predicted cascade of intermolecular charge- and energy-transfer processes, namely electron-transfer-mediated decay (ETMD) and interatomic/intermolecular Coulombic decay (ICD). An advanced coincidence technique allows us to identify several LEE-producing steps during the decay of 1s vacancies in solvated Mg2+ ions, which escaped observation in previous non-coincident experiments. We provide strong evidence for the predicted recovering of the ion’s initial state. In natural environments the recovering of the ion’s initial state is expected to cause inorganic ions to be radiation-damage hot spots, repeatedly producing destructive particles under continuous irradiation.
|
|
| 9. |
- Carravetta, Vincenzo, et al.
(författare)
-
An atomistic explanation of the ethanol-water azeotrope
- 2022
-
Ingår i: Physical Chemistry, Chemical Physics - PCCP. - : Royal Society of Chemistry (RSC). - 1463-9076 .- 1463-9084. ; 24:42, s. 26037-26045
-
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.
|
|
| 10. |
- Dupuy, Rémi, et al.
(författare)
-
The solvation shell probed by resonant intermolecular Coulombic decay
- 2024
-
Ingår i: Nature Communications. - : Nature Publishing Group. - 2041-1723. ; 15:1
-
Tidskriftsartikel (refereegranskat)abstract
- Molecules involved in solvation shells have properties differing from those of the bulk solvent, which can in turn affect reactivity. Among key properties of these molecules are their nature and electronic structure. Widely used tools to characterize this type of property are X-ray-based spectroscopies, which, however, usually lack the capability to selectively probe the solvation-shell molecules. A class of X-ray triggered "non-local" processes has the recognized potential to provide this selectivity. Intermolecular Coulombic decay (ICD) and related processes involve neighbouring molecules in the decay of the X-ray-excited target, and are thus naturally sensitive to its immediate environment. Applying electron spectroscopy to aqueous solutions, we explore the resonant flavours of ICD and demonstrate how it can inform on the first solvation shell of excited solvated cations. One particular ICD process turns out to be a potent marker of the formation of ion pairs. Another gives a direct access to the electron binding energies of the water molecules in the first solvation shell, a quantity previously elusive to direct measurements. The resonant nature of the processes makes them readily measurable, providing powerful new spectroscopic tools. X-ray triggered non-local processes, such as Intermolecular Coulombic Decay, are shown here to selectively probe solvation-shell molecules in solution and provide new information on their electronic structure and on ion-pair formation.
|
|
