Gas phase photoisomerization of urocanic acid – a theoretical study

The photochemistry of urocanic acid is investigated theoretically by means of time-dependent density functional theory. The topology of the potential energy surface along the isomerization pathway and close to the Franck–Condon region is investigated and consequences for the photoisomerization reactions are outlined. A recently published supersonic jet spectroscopy study is reinterpreted in the light of these and earlier theoretical results to give a clear picture of the gas phase photochemistry. It is found that the photochemistry of the two isomers is fundamentally different, in contrast to the situation in solution.     

Steady vortices in plasmas and geophysical flows

A number of two-dimensional fluid models in geophysical fluid dynamics and plasma physics are examined to find out whether they have steady and localized monopole vortex solutions. A simple and general method that consists of two steps is used. First the dispersion relation is calculated, to find all possible values of the phase velocity of the linear waves. Then an integral relation that determines the center-of-mass velocity of localized structures must be found. The existence condition is that this velocity should be outside the region of linear phase velocities. After a presentation of the method, previous work on the plasma drift wave model and the shallow-water equations is reviewed. In both cases it is found that the center-of-mass velocity is larger than the maximum phase velocity of the linear waves if the amplitude is large enough, and steady localized vortices can therefore exist. New results are then obtained for a number of two-field models. For the coupled ion acoustic-drift modes in plasmas, it is found that the center-of-mass velocity depends on the ratio between the parallel ion velocity component and the electrostatic potential in the vortex. If this ratio is large enough, the vortex can be steady. For the drift-Alfven mode the "center-of-charge" velocity is proportional to the ratio between the parallel current and the total charge in the vortex. It can therefore be steady if this ratio satisfies the appropriate conditions. For the quasigeostrophic two-layer equations, describing stratified flow on a rotating planet, it is found that the center-of-mass velocity is determined by the ratio between the baroclinic and the barotropic components in the vortex. If a baroclinic component with an appropriate sign is added to a barotropic vortex, it propagates faster than the barotropic Rossby waves, and can be steady. Finally, the existence conditions for a vortex in an external zonal flow are examined. It is found that the center-of-mass velocity acquires an additional westward contribution in an anticyclonic shear zone in the framework of the shallow-water equations, and also that an easterly jet south of this shear zone partly shields a vortex situated in the shear zone from the dispersive influence of the fast Rossby waves on the equatorward side.     

Discovery and high-throughput screening of heteroleptic iridium complexes for photoinduced hydrogen production

The catalytic process of photoinduced hydrogen generation via the reduction of water has been investigated. The use of parallel synthetic techniques has facilitated the synthesis of a 32 member library of heteroleptic iridium complexes that was screened, using high-throughput photophysical techniques, to identify six potential photosensitizers for use in catalytic photoinduced hydrogen production. A Pd/Ni thin film hydrogen selective sensor allowed for rapid quantification of hydrogen produced via illumination of aqueous systems of the photosensitizer, tris(2,2'-dipyridyl)dichlorocobalt ([Co(bpy)(3)]Cl(2)), and triethanolamine (a sacrificial reductant) with ultra-bright light emitting diodes (LEDs). The use of an 8-well parallel photoreactor expedited the investigation of the hydrogen evolution process and facilitated mechanistic studies. All six compounds investigated produced considerably more hydrogen than commonly utilized photosensitizers and had relative quantum efficiencies of hydrogen production up to 37 times greater than that of Ru(bpy)(3)(2+).     

Thermal decomposition of RDX from reactive molecular dynamics

We use the recently developed reactive force field ReaxFF with molecular dynamics to study thermal induced chemistry in RDX [cyclic-[CH(2)N(NO(2))](3)] at various temperatures and densities. We find that the time evolution of the potential energy can be described reasonably well with a single exponential function from which we obtain an overall characteristic time of decomposition that increases with decreasing density and shows an Arrhenius temperature dependence. These characteristic timescales are in reasonable quantitative agreement with experimental measurements in a similar energetic material, HMX [cyclic-[CH(2)N(NO(2))](4)]. Our simulations show that the equilibrium population of CO and CO(2) (as well as their time evolution) depend strongly of density: at low density almost all carbon atoms form CO molecules; as the density increases larger aggregates of carbon appear leading to a C deficient gas phase and the appearance of CO(2) molecules. The equilibrium populations of N(2) and H(2)O are more insensitive with respect to density and form in the early stages of the decomposition process with similar timescales.     

Differential capacity curves at adsorption of organic ions: Model approach I

Theoretical analysis of the double-layer model has been carried out in the presence of the specific adsorption of organic cations accompanied by considerable increase of the inner-layer dimensions. The formulae for calculation of the differential capacity curves of an electrode have been derived. A flat minimum at high negative charges, caused by the diffuse structure of the double layer, has been predicted on the capacity curves. The presence of such minima has been verified experimentally on the mercury and bismuth electrodes. By computer calculation it has been shown that, although. relatively good agreement of the theoretically calculated capacity curves with the experimental curves could he obtained, a physically unrealistic interaction parameter of the specifically adsorbed ions had to be used. As demonstrated, this result is a result of the double-layer model assuming linear dependence of the inner-layer integral capacity of the surface coverage and its independence from the electrode charge.     

Reactive scattering of sodium clusters with molecular oxygen

The first reactive differential scattering study for atomic clusters is reported. Oxidation of Na _x (x8) with O₂ is investigated in a crossed beam apparatus. Sodium oxide (Na _n O,n4) and sodium dioxide (Na _n O₂,n6) are produced with a total reactive cross section from 50 to 80 Ų, depending on the cluster size. The excess energies for these reactions are estimated by an SCF type ab initio calculation and range from 0.5 to 5 eV. The large cross section may then be understood quantitatively in terms of a harpooning mechanism as a first step in the reaction path. Angular distributions have been determined for the most abundant products, showing strong forward scattering. Two different schemes are discussed for the reaction: while the dioxides Na _n O₂ may be formed by an evaporative cooling process from a highly excited collision complex, formation of Na _n O appears to originate from a direct process. In both cases the experimental data suggest that most of the exothermicity remains in the reaction products.     

Influence of hydrolyzable metal ions on the interfacial chemistry, particle interactions, and dewatering behavior of kaolinite dispersions

The influence of hydrolyzable metal ions (Mn(II) and Ca(II)) adsorption on the surface chemistry, particle interactions, flocculation, and dewatering behavior of kaolinite dispersions has been investigated at pH 7.5 and 10.5. Metal ion adsorption was strongly cation type- and pH-dependent and significantly influenced the zeta potential, anionic polyacrylamide-acrylate flocculant (PAM) adsorption, shear yield stress, settling rate, and consolidation of kaolinite slurries. The presence of Mn(II) and Ca(II) ions alone led to a systematic reduction in zeta potential due to specific adsorption of positively charged metal ion-based hydrolysis products at the kaolinite-water interface. Metal ion-mediated zeta potential changes were reflected by lower dispersion shear yield stresses and improved clarification (higher settling rates) but had no detectable effect on dispersion consolidation. The adsorption of PAM was significantly improved by prior addition of the metal ions. In the presence of Mn(II) or Ca(II) ions, the flocculant adsorption density was enhanced at pH 7.5 for Mn(II) and pH 10.5 for Ca(II). Optimum flocculation conditions, involving partial rather than complete particle surface coverage by both metal ions and flocculant, were identified. As a consequence, the metal ions and flocculant acted synergistically to enhance dewatering, producing particle interactions that were more conducive to high settling rates and greater consolidation of kaolinite dispersions at pH 7.5 than 10.5.     

Analytical characterization of a facile porous polymer monolithic trypsin microreactor enabling peptide mass mapping using mass spectrometry

A simple and rapid single-step method is presented to fabricate an enzyme reactor using trypsin immobilized on a macroporous polymer monolith. A reactor produced in a capillary format is ready to use within 1 h of preparation. The monomers making up the monolith, including N-acryloxysuccinimide for covalent immobilization of the enzyme, are mixed with trypsin and introduced into the column by capillary force for polymerization/immobilization. The enzyme activity from column-to-column is reproducible below 5% relative standard deviation (RSD), while the reactor is durable for at least 20 weeks when stored at room temperature. The apparent kinetic constants V(max) and K(m) are of value similar to those obtained by free trypsin in solution. Enzymatic digestion of proteins was shown to be feasible on a time-scale of seconds and submicromolar concentrations enabling peptide mass mapping by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.