Neutron quasi-elastic scattering in disordered solids: a Monte Carlo study of metal-hydrogen systems

The dynamic structure factor of neutron quasi-elastic scattering has been calculated by Monte Carlo methods for atoms diffusing on a disordered lattice. The disorder includes not only variation in the distances between neighbouring atomic sites but also variation in the hopping rate associated with each site. The presence of the disorder, particularly the hopping rate disorder, causes changes in the time-dependent intermediate scattering function which translate into a significant increase in the intensity in the wings of the quasi-elastic spectrum as compared with the Lorentzian form. The effect is particularly marked at high values of the momentum transfer and at site occupancies of the order of unity. The MC calculations demonstrate how the degree of disorder may be derived from experimental measurements of the quasi-elastic scattering. The model structure factors are compared with the experimental quasi-elastic spectrum of an amorphous metal-hydrogen alloy.

Metal oxide photoanodes for solar hydrogen production

The development of sustainable hydrogen production is a key target in the further facilitation of a hydrogen economy. Solar hydrogen generation through the photolytic splitting of water sensitised by semiconductor materials is attractive as it is both renewable and does not lead to problematic by-products, unlike current hydrogen sources such as natural gas. Consequently, the development of these semiconductor materials has undergone considerable research since their discovery over 30 years ago and it would seem prescient to review the more practical results of this research. Among the critical factors influencing the choice of semiconductor material for photoelectrolysis of water are the band-gap energies, flat band potentials and stability towards photocorrosion; the latter of these points directs us to focus on metal oxides. Careful design of thin films of photocatalyst material can eliminate potential routes of losses in performance, i.e., recombination at grain boundaries. Methods to overcome these problems are discussed such as coupling a photoanode for photolysis of water to a photovoltaic cell in a 'tandem cell' device.

Vibrational spectra of α-amino acids in the zwitterionic state in aqueous solution and the solid state: DFT calculations and the influence of hydrogen bonding

The zwitterionic forms of the two simplest alpha-amino acids, glycine and l-alanine, in aqueous solution and the solid state have been modeled by DFT calculations. Calculations of the structures in the solid state, using PW91 or PBE functionals, are in good agreement with the reported crystal structures, and the vibrational spectra computed at the optimized geometries provide a good fit to the observed IR and Raman spectra in the solid state. DFT calculations of the structures and vibrational spectra of the zwitterions in aqueous solution at the B3-LYP/cc-pVDZ level were found to require both explicit and implicit solvation models. Explicit solvation was modeled by inclusion of five hydrogen-bonded water molecules attached to each of the five possible hydrogen-bonding sites in the zwitterion and the integration equation formalism polarizable continuum model (IEF-PCM) was employed, providing a satisfactory fit to observed IR and Raman spectra. Band assignments are reported in terms of potential-energy distributions, which differ in some respects to those previously reported for glycine and l-alanine.

Water sorption/desorption in polyacid-modified composite resins for dentistry

The water sorption and desorption behaviour of three commercial polyacid-modified composite resins used in clinical dentistry have been studied in detail. Cured specimens of each material were subjected to two successive water uptake cycles in an atmosphere of 93% relative humidity, with one intervening desorption cycle in a desiccating atmosphere over concentrated sulfuric acid. Specimens were found to absorb and desorb water according Fick's law until Mt/M(infinity) values of approximately 0.5. Diffusion rates for uptake varied between cycles, ranging from 2.37-4.53 x 10(-9 )cm(2) s(-1) for 1st cycle to 0.85-2.72 x 10(-8 )cm(2 )s(-1) for 2nd cycle. Desorption rates were similar to those for 2nd cycle sorption, and ranged from 0.86 to 5.47 x 10(-8 )cm(2 )s(-1). Equilibration times for 1st cycle water uptake were greater than for 2nd cycle sorption and for desorption and overall the behaviour of polyacid-modified composites in a high humidity atmosphere was similar to that of conventional composites in water. It is concluded that the hydrophilic components of the former do not bring about an enhanced rate of water transport.