The distribution and protonation states of amino acids in water droplets are of considerable concern in studies on the formation of clouds in the atmosphere as well as in many biological contexts. In the present work we use the amino acid cysteine as a prototypical example and explore the protonation states of this molecule in aqueous solution, which are strongly affected by the acidity of the environment and also can show different distributions between surface and bulk. We use a combination of X-ray photoelectron chemical shift measurements, density functional theory calculations of the shifts, and reactive force field molecular dynamics simulations of the underlying structural dynamics. We explore how the photoelectron spectra distinctly reflect the different protonation states that are generated by variation of the solution acidity and how the distribution of these protonation states can differ between bulk and surface regions. At specific pH values, we find that the distribution of the cysteine species at the surface is quite different from that in bulk, in particular, for the appearance in the surface region of species which do not exist in bulk. Some ramifications of this finding are discussed.

The debate around the oxidation states occurring in laboratory-prepared tin-oxide samples has been for a long time an obstacle for an unambiguous assignment of characterization studies performed on such samples. In particular the changes in the Sn core-level energies caused by oxidation - i.e. the chemical shifts - as measured by photoelectron spectroscopy (PES) have been under discussion. The assignment problem is especially pronounced for nanoscale structures, which are important for photovoltaics, electronics, catalysis, and gas sensing. The reasons for the difficulties lie both in the natural properties of tin oxides, which can have substantial deficiencies of oxygen and tin in the lattice, and in the shortcomings of the fabrication and PES-characterization procedures themselves. Our recent PES study on tin-oxide nanoparticles fabricated by vapour-aggregation gave a chemical shift two times larger than earlier reported for Sn(iv) oxide for the Sn 4d level. The implemented fabrication technique forms an in-vacuum beam of particles whose composition can be both controlled and characterized by PES. In the present work SnO and SnO2 nanoparticles fabricated this way were deposited from the beam and probed by PES directly, as well as after exposure to air. The deposited nanoparticle films were also imaged by TEM (Transmission Electron Microscopy). The effects of the deposition process and exposure to air on the chemical composition were studied. The PES study of deposited SnO2 nanoparticles in the Sn 4d and Sn 3d core-level regions revealed the same core level shift as for unsupported nanoparticles, indicating that the chemical composition is preserved in the deposition process. The TEM study demonstrated a crystalline structure of separate SnO2 particles with lattice constants close to the macroscopic Sn(iv)-oxide. The PES study on the particles exposed to air showed changes in the composition. For the film of initially SnO particles a higher intermediate oxide was created. For the SnO2 nanoparticle film a lower, but strong, intermediate oxide was observed, likely at the surface.

In Ag-Cu oxides possible to fabricate so far, superconductivity has not been detected, but high conductivity was. In the quest for superconductivity the demand is to create a high and peculiar copper-oxygen coordination. Such coordination makes it non-trivial to determine Cu oxidation states, which may be several and co-existing. Another reason for uncertainty is in oxygen deficiency typical for superconducting crystals. Finally, Cu oxidation is influenced by the other metals in the substance. For chemical fabrication the difficulty is to tune the relative abundances of elements in a fine way. Ag-Cu oxides have been also produced by reactive co-sputtering of Cu and Ag, but the composition with high Cu oxidation states necessary for high conductivity has not been realized. In the present work we have fabricated Ag-Cu-oxide nanoparticles containing Cu and Ag in high oxidation states actual for superconductivity. The fabrication includes reactive sputtering of Ag and Cu metals, their vapour oxidation and aggregation into nanoparticles. The ability to create different and high oxidation states, also co-existing, is demonstrated. The fabrication approach also allows overcoming the poor miscibility of Cu and Ag. The nanoparticle composition and the oxidation states could be determined due to an experimental arrangement in which photoelectron spectroscopy is applied to free nanoparticles in a beam in vacuum, what allows avoiding any contact of the particles to a substrate or atmosphere. The combination of the fabrication and characterization methods has proven to be a powerful approach when fine composition tuning and control are desirable.

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.

Intermolecular Coulombic decay (ICD) is a ubiquitous relaxation channel of electronically excited states in weakly bound systems, ranging from dimers to liquids. As it is driven by electron correlation, it was assumed that it will dominate over more established energy loss mechanisms, for example fluorescence. Here, we use electron-electron coincidence spectroscopy to determine the efficiency of the ICD process after 2a(1) ionization in water clusters. We show that this efficiency is surprisingly low for small water clusters and that it gradually increases to 40-50% for clusters with hundreds of water units. Ab initio molecular dynamics simulations reveal that proton transfer between neighboring water molecules proceeds on the same timescale as ICD and leads to a configuration in which the ICD channel is closed. This conclusion is further supported by experimental results from deuterated water. Combining experiment and theory, we infer an intrinsic ICD lifetime of 12-52 fs for small water clusters.

Acid-base equilibria of carboxylic acids and alkyl amines in the aqueous surface region were studied using surface-sensitive X-ray photoelectron spectroscopy and molecular dynamics simulations. Solutions of these organic compounds were examined as a function of pH, concentration and chain length to investigate the distribution of acid and base form in the surface region as compared to the aqueous bulk. Results from these experiments show that the neutral forms of the studied acid-base pairs are strongly enriched in the aqueous surface region. Moreover, we show that for species with at least four carbon atoms in their alkyl-chain, their charged forms are also found to be abundant in the surface region. Using a combination of XPS and MD results, a model is proposed that effectively describes the surface composition. Resulting absolute surface concentration estimations show clearly that the total organic mole fractions in the surface region change drastically as a function of solution pH. The origin of the observed surface phenomena, hydronium/hydroxide concentrations in the aqueous surface region and why standard chemical equations, used to describe equilibria in dilute bulk solution are not valid in the aqueous surface region, are discussed in detail. The reported results are of considerable importance especially for the detailed understanding of properties of small aqueous droplets that can be found in the atmosphere.

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.

Binary rare gas clusters; xenon and neon which have a significant contrariety between sizes, produced by a co-expansion set up and have been studied using synchrotron radiation based x-ray photoelectron spectroscopy. Concentration ratios of the heterogeneous clusters; 1%, 3%, 5% and 10% were controlled. The core level spectra were used to determine structure of the mixed cluster and analyzed by considering screening mechanisms. Furthermore, electron binding energy shift calculations demonstrated cluster aggregation models which may occur in such process. The results showed that in the case of low mixing ratios of 3% and 5% of xenon in neon, the geometric structures exhibit xenon in the center and xenon/neon interfaced in the outer shells. However, neon cluster vanished when the concentration of xenon was increased to 10%.

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.