MULTIMODE quantum calculations of intramolecular vibrational energies of the water dimer and trimer using ab initio-based potential energy surfaces

We report vibrational configuration interaction calculations of the monomer fundamentals of (H2O)(2), (D2O)(2), (H2O)(3), and (D2O)(3) using the code MULTIMODE and full dimensional ab initio-based global potential energies surfaces (PESs). For the dimer the HBB PES [Huang , J. Chem. Phys 128, 034312 (2008)] is used and for the trimer a new PES, reported here, is used. The salient properties of the new trimer PES are presented and compared to previous single-point calculations and the vibrational energies are compared with experiments. (C) 2008 American Institute of Physics.

Risky attitudes towards road use in pre-drivers

Motor vehicle accidents are one of the principal causes of adolescent disability or mortality and male drivers are more likely to be involved in road accidents than female drivers. In part such associations between driver age and sex have been linked to differences in risky behaviour (e.g. speed, violations) and individual characteristics (e.g. sensation seeking, deviant behaviour). The aim of this research is to determine whether associations between risky road user behaviour and individual characteristics are a function of driver behaviour or whether they are intrinsic and measurable in individuals too young to drive. Five hundred and sixty-seven pre-driver students aged 11-16 from three secondary schools completed questionnaires measuring enthusiasm for speed, sensation seeking, deviant behaviour and attitudes towards driver violations. Boys reported more risky attitudes than girls for all measures. Associations between sensation seeking, deviant behaviour and attitudes towards risky road use were present from early adolescence and were strongest around age 14, before individuals learn to drive. Risky attitudes towards road use are associated with individual characteristics and are observed in adolescents long before they learn to drive. Safe attitudes towards road use and driver behaviour should be promoted from childhood in order to be effective. (C) 2007 Elsevier Ltd. All rights reserved.

Chiral molecules on surfaces

chiral molecules can modify surfaces in many ways. Long-range chiral structures can be induced by local chirality, which can act as templates stereo-directing other molecules. Such templates are either based on the arrangement of molecules alone or involve reconstruction of the substrate suface. Stereo-direction can also be achieved buy direct local interaction between chiral moleculesx. Even the adsorption of achiral molecules onto achiral surfaces can induce local chirality due to a reduction ofsymmetry in the presence of the surface. Intrinsically chiral metal and oxide surfaces can act as templates for enantioselective adsorption and surface reactions without any surface modification.

The interplay between geometry, electronic structure, and reactivity of Cu-Ni bimetallic (111) surfaces

The mutual influence of surface geometry (e.g. lattice parameters, morphology) and electronic structure is discussed for Cu-Ni bimetallic (111) surfaces. It is found that on flat surfaces the electronic d-states of the adlayer experience very little influence from the substrate electronic structure which is due to their large separation in binding energies and the close match of Cu and Ni lattice constants. Using carbon monoxide and benzene as probe molecules, it is found that in most cases the reactivity of Cu or Ni adlayers is very similar to the corresponding (111) single crystal surfaces. Exceptions are the adsorption of CO on submonolayers of Cu on Ni(111) and the dissociation of benzene on Ni/Cu(111) which is very different from Ni(111). These differences are related to geometric factors influencing the adsorption on these surfaces.

Adsorption and dissociation of benzene on bimetallic surfaces - the influence of surface geometry and electronic structure

This topical review discusses the influence of the surface geometry (e.g. lattice parameters and termination) and electronic structure of well-defined bimetallic surfaces on the adsorption and dissociation of benzene. The available data can be divided into two categories with combinations of non-transition metals and transition metals on the one side and combinations of two transition metals on the other. The main effect of non-transition metals in surface alloys is site blocking which can suppress chemisorption and dissociation of the molecules completely. When two transition metals are combined, the effects are less dramatic. They mainly affect the strength of the chemisorption bond and the degree of dissociation due to electronic and template effects.

Variational approach in weighted Sobolev spaces to scattering by unbounded rough surfaces

We consider the problem of scattering of time harmonic acoustic waves by an unbounded sound soft surface which is assumed to lie within a finite distance of some plane. The paper is concerned with the study of an equivalent variational formulation of this problem set in a scale of weighted Sobolev spaces. We prove well-posedness of this variational formulation in an energy space with weights which extends previous results in the unweighted setting [S. Chandler-Wilde and P. Monk, SIAM J. Math. Anal., 37 (2005), pp. 598–618] to more general inhomogeneous terms in the Helmholtz equation. In particular, in the two-dimensional case, our approach covers the problem of plane wave incidence, whereas in the three-dimensional case, incident spherical and cylindrical waves can be treated. As a further application of our results, we analyze a finite section type approximation, whereby the variational problem posed on an infinite layer is approximated by a variational problem on a bounded region.

Application of interpolymer complexation to coat solid and soft surfaces

Water-soluble polymers are often capable of forming interpolymer complexes in solutions and at interfaces, which offers an excellent opportunity for surface modification. The complex formation may be driven by H-bonding between poly(carboxylic acids) and non-ionic polymers or by electrostatic attraction between oppositely-charged polyelectrolytes. In the present communication the following applications of interpolymer complexation in coating technologies will be considered: (1) Complexation between poly(acrylic acid) and non-ionic polymers via H-bonding was used to coat glass surfaces. It was realised using layer-by-layer deposition of IPC on glass surfaces with subsequent cross-linking of dry multilayers by thermal treatment. Depending on the glass surface functionality this complexation resulted in detachable and non-detachable hydrogel films; (2) Electrostatic layer-by-layer self-assembly between glycol chitosan and bovine serum albumin (BSA) was used to coat magnetic nanoparticles. It was demonstrated that the native structure of BSA remains unaffected by the self-assembling process.

Climate model calculations of the impact of aerosols from road transport and shipping

Road transport and shipping are copious sources of aerosols, which exert a 9 significant radiative forcing, compared to, for example, the CO2 emitted by these sectors. An 10 advanced atmospheric general circulation model, coupled to a mixed-layer ocean, is used to 11 calculate the climate response to the direct radiative forcing from such aerosols. The cases 12 considered include imposed distributions of black carbon and sulphate aerosols from road 13 transport, and sulphate aerosols from shipping; these are compared to the climate response 14 due to CO2 increases. The difficulties in calculating the climate response due to small 15 forcings are discussed, as the actual forcings have to be scaled by large amounts to enable a 16 climate response to be easily detected. Despite the much greater geographical inhomogeneity 17 in the sulphate forcing, the patterns of zonal and annual-mean surface temperature response 18 (although opposite in sign) closely resembles that resulting from homogeneous changes in 19 CO2. The surface temperature response to black carbon aerosols from road transport is shown 20 to be notably non-linear in scaling applied, probably due to the semi-direct response of clouds 21 to these aerosols. For the aerosol forcings considered here, the most widespread method of 22 calculating radiative forcing significantly overestimates their effect, relative to CO2, 23 compared to surface temperature changes calculated using the climate model.