Valence and Core Photoelectron Spectra of Aqueous I3- from Multi-Reference Quantum Chemistry.

The I3- molecule is known to undergo substantial structural reorganization upon solvation by a protic solvent, e.g., water. However, the details of this process are still controversially discussed in the literature. In the present study, we combined experimental and theoretical efforts to disentangle this controversy. The valence (5p), N4,5 (4d), and M4,5 (3d) edge photoelectron spectra were measured in an aqueous solution and computed using high-level multi-reference methods. Our previous publication mainly focused on obtaining reliable experimental evidence, whereas in the present article, we focused primarily on theoretical aspects. The complex electronic structure of I3- requires the inclusion of both static and dynamic correlation, e.g., via the multi-configurational perturbation theory treatment. However, the resulting photoelectron spectra appear to be very sensitive to problems with variational stability and intruder states. We attempted to obtain artifact-free spectra, allowing for a more reliable interpretation of experiments. Finally, we concluded that the 3d Photoelectron Spectrum (PES) is particularly informative, evidencing an almost linear structure with a smaller degree of bond asymmetry than previously reported.

Probing the molecular structure of aqueous triiodide via X-ray photoelectron spectroscopy and correlated electron phenomena.

Liquid-microjet-based X-ray photoelectron spectroscopy was applied to aqueous triiodide solutions, I3-(aq.), to investigate the anion's valence- and core-level electronic structure, ionization dynamics, associated electron-correlation effects, and nuclear geometric structure. The roles of multi-active-electron (shake-up) ionization processes - with noted sensitivity to the solute geometric structure - were investigated through I3-(aq.) solution valence, I 4d, and I 3d core-level measurements. The experimental spectra were interpreted with the aid of simulated photoelectron spectra, built upon multi-reference ab initio electronic structure calculations associated with different I3-(aq.) molecular geometries. A comparison of the single-to-multi-active-electron ionization signal ratios extracted from the experimental and theoretical core-level photoemission spectra suggests that the ground state of the solute adopts a near-linear average geometry in aqueous solutions. This contrasts with the interpretation of time-resolved X-ray solution scattering studies, but is found to be fully consistent with the rest of the solution-phase I3-(aq.) literature. Comparing the results of low- and high-photon-energy photoemission measurements, we further suggest that the aqueous anion adopts a more asymmetric geometry at the aqueous-solution-gas interface than in the aqueous bulk.

Reversible Water-Induced Phase Changes of Cobalt Oxide Nanoparticles.

Cobalt oxides have been identified as highly active catalysts for the electrochemical water splitting and oxygen evolution reaction. Using near-ambient pressure resonant photoelectron spectroscopy, we studied changes in the metal-oxygen coordination of size-selected core-shell CoOx nanoparticles induced by liquid water. In dry conditions, the nanoparticles exhibit an octahedrally coordinated Co2+ core and a tetrahedrally coordinated Co2+ shell. In the presence of liquid water, we observe a reversible phase change of the nanoparticle shell into octahedrally coordinated Co2+ as well as partially oxidized octahedrally coordinated Co3+. This is in contrast to previous findings, suggesting an irreversible phase change of tetrahedrally coordinated Co2+ after the oxygen evolution reaction conditioning. Our results demonstrate the appearance of water-induced structural changes different from voltage-induced changes and help us to understand the atomic scale interaction of CoOx nanoparticles with water in electrochemical processes.

Photoelectron spectra of alkali metal-ammonia microjets: From blue electrolyte to bronze metal.

Experimental studies of the electronic structure of excess electrons in liquids-archetypal quantum solutes-have been largely restricted to very dilute electron concentrations. We overcame this limitation by applying soft x-ray photoelectron spectroscopy to characterize excess electrons originating from steadily increasing amounts of alkali metals dissolved in refrigerated liquid ammonia microjets. As concentration rises, a narrow peak at ~2 electron volts, corresponding to vertical photodetachment of localized solvated electrons and dielectrons, transforms continuously into a band with a sharp Fermi edge accompanied by a plasmon peak, characteristic of delocalized metallic electrons. Through our experimental approach combined with ab initio calculations of localized electrons and dielectrons, we obtain a clear picture of the energetics and density of states of the ammoniated electrons over the gradual transition from dilute blue electrolytes to concentrated bronze metallic solutions.

Valence and Core-Level X-ray Photoelectron Spectroscopy of a Liquid Ammonia Microjet.

Photoelectron spectroscopy of microjets expanded into vacuum allows access to orbital energies for solute or solvent molecules in the liquid phase. Microjets of water, acetonitrile and alcohols have previously been studied; however, it has been unclear whether jets of low temperature molecular solvents could be realized. Here we demonstrate a stable 20 µm jet of liquid ammonia (-60 °C) in a vacuum, which we use to record both valence and core-level band photoelectron spectra using soft X-ray synchrotron radiation. Significant shifts from isolated ammonia in the gas-phase are observed, as is the liquid-phase photoelectron angular anisotropy. Comparisons with spectra of ammonia in clusters and the solid phase, as well as spectra for water in various phases potentially reveal how hydrogen bonding is reflected in the condensed phase electronic structure.

Use of δ13C values to determine vegetation selectivity in East African herbivores.

The quantitative plant species composition of the rumen contents of a large number of individuals from eight East African herbivores was determined by direct visual analysis. All plant species were classified as either C3 or C4, and an estimated δ13C for the rumen sample was calculated. This estimated value was compared to a measured value determined directly from rumen subsample. The two methods of determining quantitative C3 and C4 composition differed by less than 1%, and the isotopic analysis has the advantage of being rapid and totally objective.The isotopic analysis allowed us to differentiate between grazers and browsers and to determine the quantitative dependence of each animal on C3 and C4 photosynthetic types. Kongoni, wildebeest, cattle, and sheep were nearly pure grazers on the Athi Kapiti Plains; and the Grant's gazelle were predominantly browsers. Thompson's gazelle, goast and impala were intermediate. The species most dependent upon browse showed a marked and rapid shift to grass within a few days following rain. This isotopic method may have general utility in the study of East African ecology.