Nonstoichiometric intensities in core photoelectron spectroscopy.

X-ray photoemission spectroscopy is used in a great variety of research fields; one observable is the sample's stoichiometry. The stoichiometry can be deduced based on the expectation that the ionization cross sections for innershell orbitals are independent of the molecular composition. Here we used chlorine-substituted ethanes in the gas phase to investigate the apparent carbon stoichiometry. We observe a nonstoichiometric ratio for a wide range of photon energies, the ratio exhibits x-ray-absorption fine structure spectroscopy (EXAFS)-like oscillations and hundreds of eV above the C1s ionization approaches a value far from 1. These effects can be accounted for by considering the scattering of the outgoing photoelectron, which we model by multiple-scattering EXAFS calculations, and by considering the effects of losses due to monopole shakeup and shakeoff and to intramolecular inelastic scattering processes.

Size of free neutral CO2 clusters from carbon 1s ionization energies.

Free neutral CO(2) clusters were produced by adiabatic expansion and characterized by carbon 1s (C1s) photoelectron spectroscopy using synchrotron radiation. The shift in C1s ionization energy (IE) between the cluster and the monomer, i.e., ΔIE = IE(cluster) - IE(monomer), was found to vary systematically with the experimental conditions. A functional relationship is established between the mean cluster size in the beam, , and ΔIE, in good agreement with theoretical calculations of shifts in ionization energy for model clusters. This makes it possible to use core-level photoelectron spectroscopy to monitor the mean cluster size and also to estimate from expansion conditions.

Concentrations of mercury and other toxic elements in orange roughy, Hoplostethus atlanticus, from the Mid-Atlantic Ridge.

Concentrations of the elements mercury, arsenic, cadmium and lead were measured in the muscle tissue of Orange roughy (Hoplostethus atlanticus) obtained from the Mid-Atlantic Ridge during the MAR: -ECO: expedition in the North Atlantic Ocean in 2004. The age of the fish varied from 1 to 139 years. To the best of our knowledge, the concentration of the heavy metals presented here is for one of the oldest fish in the literature, in addition to the fact that very little information on arsenic in Orange roughy has been previously published. The concentration of mercury in the fillet of the fish varied between 0.06 and 1.1 µg g⁻¹ w.w. Mercury was the only element that was positively correlated to the age. The concentrations of mercury were found to be below the maximum limits for Orange roughy set by EU at 1.0 µg g⁻¹ w.w, except for a 134 year fish sample with a concentration of 1.1 µg g⁻¹ w.w.

Valence photoelectron spectroscopy of N2 and CO: recoil-induced rotational excitation, relative intensities, and atomic orbital composition of molecular orbitals.

Recoil-induced rotational excitation accompanying photoionization has been measured for the X, A, and B states of N(2)(+) and CO(+) over a range of photon energies from 60 to 900 eV. The mean recoil excitation increases linearly with the kinetic energy of the photoelectron, with slopes ranging from 0.73×10(-5) to 1.40×10(-5). These slopes are generally (but not completely) in accord with a simple model that treats the electrons as if they were emitted from isolated atoms. This treatment takes into account the atom from which the electron is emitted, the molecular-frame angular distribution of the electron, and the dependence of the photoelectron cross section on photon energy, on atomic identity, and on the type of atomic orbital from which the electron is ejected. These measurements thus provide a tool for investigating the atomic orbital composition of the molecular orbitals. Additional insight into this composition is obtained from the relative intensities of the various photolines in the spectrum and their variation with photon energy. Although there are some discrepancies between the predictions of the model and the observations, many of these can be understood qualitatively from a comparison of atomic and molecular wavefunctions. A quantum-mechanical treatment of recoil-induced excitation predicts an oscillatory variation with photon energy of the excitation. However, the predicted oscillations are small compared with the uncertainties in the data, and, as a result, the currently available results cannot provide confirmation of the quantum-mechanical theory.

Effects of molecular conformation on inner-shell ionization energies.

Experimental evidence for an effect of molecular conformation on inner-shell ionization energies has been observed for the first time. Examples are seen in the carbon 1s spectra of butyronitrile, 1-fluoropropane, and propanal, and other similar molecules. At room temperature these exist in two different conformations, with different distances and, hence, different Coulombic interactions between the negatively charged electronegative group and the methyl carbon. The experimental results are in accord with theoretical predictions with respect to both ionization energies and populations of the different conformers.

Lineshapes in carbon 1s photoelectron spectra of methanol clusters.

A general protocol for theoretical modeling of inner-shell photoelectron spectra of molecular clusters is presented and applied to C1s spectra of oligomers and medium-sized clusters of methanol. The protocol employs molecular dynamics for obtaining cluster geometries and a polarizable force field for computing site-specific chemical shifts in ionization energy and linewidth. Comparisons to spectra computed from first-principle theories are used to establish the accuracy of the proposed force field approach. The model is used to analyze the C1s photoelectron spectrum of medium-sized clusters in terms of surface and bulk contributions. By treating the surface-to-bulk ratio as an adjustable parameter, satisfactory fits are obtained to experimental C1s spectra of a beam of methanol clusters.

Size of neutral argon clusters from core-level photoelectron spectroscopy.

Theoretical models of lineshapes in Ar2p photoionization spectra have been calculated for free, neutral argon clusters of different sizes. The lineshape models are fitted to experimental spectra and used to estimate the mean cluster size realized in the experiment. The results indicate that size estimators working from stagnation conditions [R. Karnbach, M. Joppien, J. Stapelfeldt, J. Wörmer and T.Möller, Rev. Sci. Instrum., 1993, 64, 2838] may underestimate the mean cluster size.

Conformational effects in inner-shell photoelectron spectroscopy of ethanol.

The carbon 1s photoelectron spectrum of ethanol shows two peaks, one for the methyl carbon and one for the functionalized carbon. While the peak shape for the functionalized carbon is readily understood, the shape for the methyl carbon requires that there be comparable contributions from both the anti and gauche conformers of ethanol and that the torsional motion in the HOCC dihedral angle be strongly excited upon core ionization. An accurate description of the peak shape requires a high level of electronic-structure theory together with consideration of anharmonicity and coupling of the torsional motion with other vibrational modes.

The electronic structure of free water clusters probed by Auger electron spectroscopy.

(H2O)(N) clusters generated in a supersonic expansion source with N approximately 1000 were core ionized by synchrotron radiation, giving rise to core-level photoelectron and Auger electron spectra (AES), free from charging effects. The AES is interpreted as being intermediate between the molecular and solid water spectra showing broadened bands as well as a significant shoulder at high kinetic energy. Qualitative considerations as well as ab initio calculations explain this shoulder to be due to delocalized final states in which the two valence holes are mostly located at different water molecules. The ab initio calculations show that valence hole configurations with both valence holes at the core-ionized water molecule are admixed to these final states and give rise to their intensity in the AES. Density-functional investigations of model systems for the doubly ionized final states--the water dimer and a 20-molecule water cluster--were performed to analyze the localization of the two valence holes in the electronic ground states. Whereas these holes are preferentially located at the same water molecule in the dimer, they are delocalized in the cluster showing a preference of the holes for surface molecules. The calculated double-ionization potential of the cluster (22.1 eV) is in reasonable agreement with the low-energy limit of the delocalized hole shoulder in the AES.

Anomalous natural linewidth in the 2p photoelectron spectrum of SiF4.

The silicon 2p photoelectron spectra for SiH4, SiF4, and SiCl4 have been analyzed to give the natural linewidths of the Si 2p hole states, which reflect the Auger decay rates of the states. For SiH4 the measured width of 38 meV is in approximate agreement with the prediction of the one-center model (32 meV), but that for SiF4 of 79 meV is more than 5 times the value of 14 meV predicted by this model. Approximate theoretical calculations indicate that valence electrons from the fluorine atoms of SiF4 play an important role in the Auger decay via interatomic processes.

Cadmium, lead, copper and zinc in blue mussels (Mytilus edulis) sampled in the Hardangerfjord, Norway.

Cadmium, lead, copper and zinc were determined in the soft tissues of blue mussels (Mytilus edulis) sampled from four locations along the Hardangerfjord in western Norway. A source of pollution is located at the head of the fjord and the sampling was performed at various distances from this source. The results obtained in this study (1998) were compared with results from similar studies carried out in 1983 and 1992. The mean cadmium concentrations in blue mussels sampled at Måge (13 km from the source of pollution) were approximately 18 mg kg-1 fresh weight in 1983, 2.4 mg kg-1 fresh weight in 1992 and 1.1 mg kg-1 fresh weight in 1998. The mean cadmium concentrations in blue mussels sampled at Varaldsøy (105 km from the source of pollution) were approximately 5 mg kg-1 fresh weight in 1983, 0.5 mg kg-1 fresh weight in 1992 and 0.4 mg kg-1 fresh weight in 1998. The mean lead concentration in blue mussels sampled at Måge was 140 mg kg-1 fresh weight in 1983. The mean lead concentrations in 1992 and 1998 had decreased to 6 and 3 mg kg-1 fresh weight, respectively. The mean lead concentrations in blue mussels from Gravdal were 15 mg kg-1 fresh weight in 1982, 1 mg kg-1 in 1992 and less than 1 mg kg-1 fresh weight in 1998. The mean copper concentrations in blue mussels were relatively constant over this period at all locations, with a variation between 0.6 and 1.2 mg kg-1 fresh weight. The mean zinc concentration in blue mussels sampled at Måge decreased from 120 to 30 mg kg-1 fresh weight in the period between 1983 and 1998.

Chemical insights from high-resolution X-ray photoelectron spectroscopy and ab initio theory: propyne, trifluoropropyne, and ethynylsulfur pentafluoride.

High-resolution carbon 1s photoelectron spectroscopy of propyne (HC triple bond CCH3) shows a spectrum in which the contributions from the three chemically inequivalent carbons are clearly resolved and marked by distinct vibrational structure. This structure is well accounted for by ab initio theory. For 3,3,3-trifluoropropyne (HC triple bond CCF3) and ethynylsulfur pentafluoride (HC triple bond CSF5), the ethynyl carbons show only a broad structure and have energies that differ only slightly from one another. The core-ionization energies can be qualitatively understood in terms of conventional resonance structures; the vibrational broadening for the fluorinated compounds can be understood in terms of the effects of the electronegative fluorines on the charge distribution. Combining the experimental results with gas-phase acidities and with ab initio calculations provides insights into the effects of initial-state charge distribution and final-state charge redistribution on ionization energies and acidities. In particular, these considerations make it possible to understand the apparent paradox that SF5 and CF3 have much larger electronegativity effects on acidity than they have on carbon 1s ionization energies.