Atmospheric chemistry of diazomethane – an experimental and theoretical study

The kinetics of the O₃, OH and NO₃ radical reactions with diazomethane were studied in smog chamber experiments employing long-path FTIR and PTR-ToF-MS detection. The rate coefficients were determined to be k _CH2NN+O3?=?(3.2?±?0.4)?×?10^?17 and k _CH2NN+OH?=?(1.68?±?0.12)?×?10^?10 cm³ molecule^?1 s^?1 at 295?±?3?K and 1013?±?30 hPa, whereas the CH₂NN?+?NO₃ reaction was too fast to be determined in the static smog chamber experiments. Formaldehyde was the sole product observed in all the reactions. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ calculations showing the reactions to proceed exclusively via addition to the carbon atom. The atmospheric fate of diazomethane is discussed.     

Coupling of equivalent particles in a field of given symmetry

A formula of Kotani for the coupling of equivalent particles in a field of a given symmetry is rederived using group algebraic methods.     

State vectors and propagators in many-electron theory. A unified approach

A unitary group formulation of the many-electron problem is employed to give explicit representations of state vectors which are convenient for the discussion of progerties derived from propagatorcalculations. New results are obtained concerning the nature of various random-phase-like approximations and ground state representatives are generated from consistency requirements for the spectral resolution of the polarization propagator. The explicit solution admits the calculation of ground state average values for arbitrary operators and a variational upper bound to the ground state energy.     

On the projection of many-electron spin eigenstates

A translation is made of spin projection methods into the language of second quantization. This leads to a new formula for the Sanibel coefficients and expressions convenient to use for automatic calculation of spin projections.     

Electron propagator calculations of molecular electron affinities

An approximate electron propagator method for predictive calculations of molecular electron affinities is proposed. The self-energy accounts for relaxation effects to all orders Additional correlation effects are treated using a diagonal approximation with shifted denominators. Applications to CN, NH₂, and PH₂ are reported.     

Structural and electrical properties of γ-alumina - lithium sulphate films

Li₂SO₄ as a model ionic conductor has received very much attention over several decades. Especially, in recent years Li₂SO₄ and Li₂SO₄-Al₂O₃ have been mentioned as promising proton conducting electrolytes for applications such as intermediate temperature fuel cells and novel cogeneration systems regarding H₂S handling devices. This has encouraged us to strive towards further improvement of the properties of the materials to meet the demands of the applications. In order to improve the properties of this system, a new process, a suspension technique, has been recently developed to prepare nanostructured powder and thin film Li₂SO₄-Al₂O₃ membranes. The powders and thin films have a well crystallised structure composed of two phases, Li₂SO₄ and γ-Al₂O₃, and excellent mechanical strength. The thin film thickness is in the scale of a few to several mm with a smooth and shining surface and a homogeneous macroscopic structure. It is a very interesting phenomenon that all samples show no significant conductivity increase at the temperature of the phase transition (∼ 577 °C) from β to α phase of pure Li₂SO₄. This transition has important significance for applications. The conductivity of the two-phase film materials has been greatly enhanced, where the xLi₂SO₄-(1-x)Al₂O₃ (x=58) sample shows the highest conductivity, about 1 S/cm at 600 °C; the activation energy decreases with increasing Li₂SO₄ content. These results agree with the so called composite effect for the conductivity enhancement observed earlier for two-phase bulk materials. Based on the four-step proton conducting mechanism in sulphate-based materials, this work may propose a new mechanism. The protons might jump in a water network associated with the water molecular re-orientation, which is accompanied with the single proton jump of the four-step transportation among SO ₄ ²⁻ groups from one Li₂SO₄ molecule to another. The former mechanism occur in the interfacial region between the Li₂SO₄ and the Al₂O₃ grains, while the latter occur in the bulk of the Li₂SO₄ grains. These thin film materials are intended for use as proton conducting ceramic membranes in applications such as desulphurisation and fuel cell co-generation plants. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Natural orbital iterations for the ground state of nitric oxide

A method for the use of natural orbital iterations in limited CI calculations is discussed. This method is then applied to the ground X₂II state of the nitric oxide molecule at its experimental equilibrium internuclear separation to yield the total energy, dipole moment, spin densities at each nucleus, and approximate natural spin orbitals for this molecule.     

Sorption of Pu(VI) onto TiO2

The sorption of Pu(VI) onto TiO(2) was studied as a function of pH (2-10) and Pu concentration (10(-8)-10(-4) M) under an N(2) atmosphere, in 0.016 and 0.1 M NaClO(4). A batch-wise method was used, in which pH was measured in separate experimental containers after removal of a sample to determine the amount of Pu that had been sorbed. As Pu is radioactive, it was used as a tracer and measured by liquid scintillation counting. No ionic strength dependence was discerned, which was taken as an indication of inner sphere complex formation. In the interval of pH 2-7 the system could be described by the formation of two positively charged surface complexes using a 1-pK Stern model. Sorption of the plutonyl ion (PuO(2)(2+)) and the first hydrolysis species (PuO(2)(OH)(+)) was estimated using FITEQL to logK(1)=6.9 and logK(2)=1.4, respectively.     

Impedance spectroscopy study of gadolinia-doped ceria

The electrical properties of Gd_0.1Ce_0.9O_1.95 were investigated in various gas atmospheres using a.c. impedance spectroscopy. In dry oxygen, impedance spectra consisted of two arcs at low temperatures corresponding to bulk and grain boundary behaviour, respectively, and only one arc at high temperatures (T>550 °C). The results showed a high oxygen ion conductivity in oxygen atmosphere more than 10⁻² S/cm at 600 °C. In water atmospheres, the bulk arc in dry oxygen was reduced by 30 %, and an additional arc corresponding to the grain boundary effect appeared. It seems that the presence of water may decrease the bulk resistance, but causes an additional grain boundary resistance and thus increase in the total resistance. In hydrogen atmosphere, a conductivity enhancement up to one order of magnitude was observed. In hydrogen there is a reduction of Ce⁴⁺ to Ce³⁺ in the sample, which involves defect formation generating e.g. electrons, additional oxygen vacancies and at the same time protons in the lattice. These new charge carriers are responsible for a significant conductivity enhancement. Therefore, in a hydrogen atmosphere the material is a mixed (oxygen ion + proton + electron) conductor. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

A new material for hydrogen storage; ScAl0.8Mg0.2

A novel aluminium rich alloy for hydrogen storage has been discovered, ScAl_0.8Mg_0.2, which has very promising properties regarding hydrogen storage capacity, kinetics and stability towards air oxidation in comparison to hydrogen absorption in state-of-the-art intermetallic compounds. The absorption of hydrogen was found to be very fast, even without adding any catalyst, and reversible. The discovered alloy crystallizes in a CsCl-type structure, but decomposes to ScH₂ and Al(Mg) during hydrogen absorption. Detailed analysis of the hydrogen absorption in ScAl_0.8Mg_0.2 has been performed using in situ synchrotron radiation powder X-ray diffraction, neutron powder diffraction and quantum mechanical calculations. The results from theory and experiments are in good agreement with each other.