Final Report for Department of Energy grant DE-FG02-91ER45455, "Theoretical Study of Reactions at the Electrode-Electrolyte Interface"

In this project, reaction rates were predicted by numerical methods, in a collaboration with Argonne National Laboratory . Emphasis is on electron transfer and transport involving ions known to be important in enhancing stress corrosion cracking in light water reactors and on electron transfer at oxide surfaces. In the latter part of the grant period we placed increased emphasis on development and use of self consistent tight binding methods for this kind of study. We showed that by careful fitting of results from first principles plane wave calculations,we could model surfaces and interfaces oxides and metals using these methods. We obtained results for the titanium/titanium oxide interface in this way and completed a model of the ruthenium dioxide surface using our innovative self consistent tight binding molecular dynamics methods. We completed development of a description of liquid water within the self consistent tight binding context and studied the rutile water 110 interface to determine if it is hydroxylated. A self consistent tight binding study of titanium metal surfaces demonstrated the usefulness of this method for metals. In collaboration with the Argonne group, we extended the tight binding calculations on rutile titania to the anatase form and made the first calculations of the relative stability of anatase and rutile as a function of crystallite size. We completed studies of small anatase particles in water using the method and found significant distortions of nanoparticle crystallite shapes as a consequence of interactions with the water

Identical Particle Scattering From A Weakly Coupled Bose-Einstein Condensed Gas

We calculate the scattering states and cross sections for a Bose-Einstein condensed dilute gas trapped in a spherical square well of finite depth. The interactions are treated in the scattering length approximation. We solve the Gross-Pitaevskii equation and the Bogoliubov equations for bound and scattering states. The results show that there are transparency effects reminiscent of those conjectured to occur for strongly coupled systems. When incident particle wavelengths λ are comparable to the well size a, exchange induced transparency enhancement is dramatic only for particular combinations of well depth, interaction strength, and particle number. For particles with large momenta (a/λ≫1),however, exchange with the condensate results in enhanced transmission for all coupling strengths. We calculated the rate of decay of the scattering states to leading order in anharmonic corrections to the Bogoliubov approximation and found the corresponding inelastic cross sections to be extremely small

High-quality variational wave functions for small 4He clusters

We report a variational calculation of ground state energies and radii for 4He_N droplets (3 \leq N \leq 40), using the atom-atom interaction HFD-B(HE). The trial wave function has a simple structure, combining two- and three-body correlation functions coming from a translationally invariant configuration-interaction description, and Jastrow-type short-range correlations. The calculated ground state energies differ by around 2% from the diffusion Monte Carlo results.Comment: 5 pages, 1 ps figure, REVTeX, submitted to Phys. Rev.

Possibility of two types of localized states in a two-dimensional disordered lattice

We report results of our numerical calculations, based on the equation of motion method, of dc electrical conductivity, and of density of states for up to 40×40 two-dimensional square lattices modeling a tight-binding Hamiltonian for a binary (AB) compound, disordered by randomly distributed B vacancies up to 10%. Our results indicate strongly localized states away from band centers separated from the relatively weakly localized states towards midband. This is in qualitative agreement with the idea of a "mobility edge" separating exponentially localized states from the power-law localized states as suggested by the two-parameter scaling theory of Kaveh in two dimensions. An alternative explanation, consistent with one-parameter scaling theory, is that the observed numerical effects may arise as a consequence of the variation of the localization length over the band

Jahn Teller Effect of Cations in Water: The Cupric Ion in Water

We report a molecular dynamics model for the Jahn Teller effect in the solvation shell of a cation in solution in an aqueous liquid. We apply the model to the cupric ion and compare results with results of neutron scattering experiments on copper chlorate solutions. We conclude that the original interpretation of the experiments in terms of a Jan Teller effect may require modification

Potential for improvement of population diet through reformulation of commonly eaten foods

Food reformulation: Reformulation of foods is considered one of the key options to achieve population nutrient goals. The compositions of many foods are modified to assist the consumer bring his or her daily diet more in line with dietary recommendations. Initiatives on food reformulation: Over the past few years the number of reformulated foods introduced on the European market has increased enormously and it is expected that this trend will continue for the coming years. Limits to food reformulation: Limitations to food reformulation in terms of choice of foods appropriate for reformulation and level of feasible reformulation relate mainly to consumer acceptance, safety aspects, technological challenges and food legislation. Impact on key nutrient intake and health: The potential impact of reformulated foods on key nutrient intake and health is obvious. Evaluation of the actual impact requires not only regular food consumption surveys, but also regular updates of the food composition table including the compositions of newly launched reformulated foods

Characteristics of starch-based films with different amylose contents plasticised by 1-ethyl-3-methylimidazolium acetate

Starch-based films plasticised by an ionic liquid, 1-ethyl-3-methylimidazolium acetate ([Emim][OAc]), were prepared by a simple compression moulding process, facilitated by the strong plasticisation effect of [Emim][OAc]. The effects of amylose content of starch (regular vs. high-amylose maize) and relative humidity (RH) during ageing of the samples on a range of structural and material characteristics were investigated. Surprisingly, plasticisation by [Emim][OAc] made the effect of amylose content insignificant, contrary to most previous studies when other plasticisers were used. In other words, [Emim][OAc] changed the underlying mechanism responsible for mechanical properties from the entanglement of starch macromolecules (mainly amylose), which has been reported as a main responsible factor previously. The crystallinity of the plasticised starch samples was low and thus was unlikely to have a major contribution to the material characteristics, although the amylose content impacted on the crystalline structure and the mobility of amorphous parts in the samples to some extent. Therefore, RH conditioning and thus the sample water content was the major factor influencing the mechanical properties, glass transition temperature, and electrical conductivity of the starch films. This suggests the potential application of ionic liquid-plasticised starch materials in areas where the control of properties by environmental RH is desired

Understanding the structural disorganization of starch in water-ionic liquid solutions

Using synchrotron X-ray scattering analyses and Fourier transform infrared spectroscopy, this work provides insights into the solvent effects of water : [C2mim][OAc] solutions on the disorganization of a starch semi-crystalline structure. When a certain ratio (10.2 : 1 mol/mol) of water : [C2mim][OAc] solution is used, the preferential hydrogen bonding between starch hydroxyls and [OAc]− anions results in the breakage of the hydrogen bonding network of starch and thus the disruption of starch lamellae. This greatly facilitates the disorganization of starch, which occurs much easier than in pure water. In contrast, when 90.8 : 1 (mol/mol) water : [C2mim][OAc] solution is used, the interactions between [OAc]− anions and water suppress the solvent effects on starch, thereby making the disorganization of starch less easy than in pure water. All these differences can be shown by changes in the lamellar and fractal structures: firstly, a preferable increase in the thickness of the crystalline lamellae rather than that of the amorphous lamellae causes an overall increase in the thickness of the semi-crystalline lamellae; then, the amorphous lamellae start to decrease probably due to the out-phasing of starch molecules from them; this forms a fractal gel on a larger scale (than the lamellae) which gradually decreases to a stable value as the temperature increases further. It is noteworthy that these changes occur at temperatures far below the transition temperature that is thermally detectable as is normally described. This hints to our future work that using certain aqueous ionic liquids for destructuration of the starch semi-crystalline structure is the key to realize green processes to obtain homogeneous amorphous materials

Identical particle scattering from a weakly coupled Bose-Einstein condensed gas

We calculate the scattering states and cross sections for a Bose-Einstein condensed dilute gas trapped in a spherical square well of finite depth. The interactions are treated in the scattering length approximation. We solve the Gross-Pitaevskii equation and the Bogoliubov equations for bound and scattering states. The results show that there are transparency effects reminiscent of those conjectured to occur for strongly coupled systems. When incident particle wavelengths λ are comparable to the well size a, exchange induced transparency enhancement is dramatic only for particular combinations of well depth, interaction strength, and particle number. For particles with large momenta (a/λ≫1),however, exchange with the condensate results in enhanced transmission for all coupling strengths. We calculated the rate of decay of the scattering states to leading order in anharmonic corrections to the Bogoliubov approximation and found the corresponding inelastic cross sections to be extremely small