Kanstruphedrick2779

We report the temperature influence of the OHad and Oad electroadsorption on RuO2(110) films grown on TiO2(110) crystals in alkaline media. From the temperature effect, we evaluate the enthalpy and entropy of the OHad and Oad electroadsorption, including the adsorbate-adsorbate interactions that we analyze using the interaction parameters of the Frumkin-isotherm model. We found that the adsorbates repel each other enthalpically but attract each other entropically. Our result suggests that an entropy analysis is necessary to capture the electroadsorption behavior on RuO2 since the enthalpy-entropy competition strongly influences the electroadsorption behavior. Our observation of an entropic force is consistent with the view that water may be a mediator for adsorbate-adsorbate interactions.Copper oxides species deposited on ceria rods, particles, and cubes were examined for low-temperature oxidation of CO. It was found that the shape of ceria altered the dispersion and chemical state of copper species considerably. CuOx monolayers and bilayers were formed on ceria rods and particles, while multilayers and faceted particles co-existed on ceria cubes. The formation of Cu+ species at the copper-ceria interface involved a significant charge transfer from copper oxides to the ceria surface via a strong electronic interaction, which was more pronounced on ceria rods. The concentrations of surface Cu+ and oxygen vacancies followed the order rods > particles > cubes, in line with their catalytic activity for CO oxidation at 343 K.The low-energy electronic states of UN and UN+ have been examined using high-level electronic structure calculations and two-color photoionization techniques. The experimental measurements provided an accurate ionization energy for UN (IE = 50 802 ± 5 cm-1). Spectra for UN+ yielded ro-vibrational constants and established that the ground state has the electronic angular momentum projection Ω = 4. Ab initio calculations were carried out using the spin-orbit state interacting approach with the complete active space second-order perturbation theory method. A series of correlation consistent basis sets were used in conjunction with small-core relativistic pseudopotentials on U to extrapolate to the complete basis set limits. The results for UN correctly obtained an Ω = 3.5 ground state and demonstrated a high density of configurationally related excited states with closely similar ro-vibrational constants. Similar results were obtained for UN+, with reduced complexity owing to the smaller number of outer-shell electrons. The calculated IE for UN was in excellent agreement with the measured value. Improved values for the dissociation energies of UN and UN+, as well as their heats of formation, were obtained using the Feller-Peterson-Dixon composite thermochemistry method, including corrections up through coupled cluster singles, doubles, triples and quadruples. An analysis of the ab initio results from the perspective of the ligand field theory shows that the patterns of electronic states for both UN and UN+ can be understood in terms of the underlying energy level structure of the atomic metal ion.The role of electronic predissociation (EP) in the dissociation dynamics of rare gas⋯dihalogen complexes (Rg⋯X2) prepared in the B electronic state was probed using ion time-of-flight velocity-map imaging. Specifically, EP of complexes prepared in the T-shaped Ar⋯I2, Ne⋯I2, He⋯I2, Ar⋯Br2, Ne⋯Br2, and He⋯Br2 levels with varying amounts of X2 vibrational excitation, ν', was investigated. The atomic I(2P3/2) or Br(2P3/2) EP fragments were probed using ion time-of-flight velocity-map imaging. Definitive evidence for EP was observed only for the Ar⋯I2 complex, and it occurs for all of the T-shaped intermolecular levels investigated, those with ν' = 12-22, 24, and 25. The relative yields for EP in these levels measured as a function of ν' are consistent with previously reported yields for the competing mechanism of vibrational predissociation. The anisotropies of the I+ images collected for Ar⋯I2 indicate that EP is occurring on timescales shorter than the rotational periods of the complex. The kinetic energy distributions of the departing I-atom fragments suggest that EP occurs from an asymmetric geometry rather than the rigid T-shaped geometry for many of the Ar⋯I2 levels prepared. PLX-4720 datasheet These findings indicate that intramolecular vibrational redistribution of these initially prepared T-shaped levels to excited levels bound within a lower-energy intermolecular potential occurs prior to EP.We present a brief pedagogical review of theoretical Green's function methods applicable to open quantum systems out of equilibrium, in general, and single molecule junctions, in particular. We briefly describe experimental advances in molecular electronics and then discuss different theoretical approaches. We then focus on Green's function methods. Two characteristic energy scales governing the physics are many-body interactions within the junctions and molecule-contact coupling. We, therefore, discuss weak interactions and weak coupling as two limits that can be conveniently treated within, respectively, the standard nonequilibrium Green's function (NEGF) method and its many-body flavors (pseudoparticle and Hubbard NEGF). We argue that the intermediate regime, where the two energy scales are comparable, can in many cases be efficiently treated within the recently introduced superperturbation dual fermion approach. Finally, we review approaches for going beyond these analytically accessible limits, as embodied by recent developments in numerically exact methods based on Green's functions.Accurate calculation of the ion-ion recombination rate coefficient has been of long-standing interest as it controls the ion concentration in gas phase systems and in aerosols. We describe the development of a hybrid continuum-molecular dynamics (MD) approach to determine the ion-ion recombination rate coefficient. This approach is based on the limiting sphere method classically used for transition regime collision phenomena in aerosols. When ions are sufficiently far from one another, the ion-ion relative motion is described by diffusion equations, while within a critical distance, MD simulations are used to model ion-ion motion. MD simulations are parameterized using the Assisted Model Building with Energy Refinement force-field as well as by considering partial charges on atoms. Ion-neutral gas collisions are modeled in two mutually exclusive cubic domains composed of 103 gas atoms each, which remain centered on the recombining ions throughout calculations. Example calculations are reported for NH4+ recombination with NO2- in He, across a pressure range from 10 kPa to 10 000 kPa.