The (2√3×3)rect. phase of alkylthiolate self-assembled monolayers on Au(111): a symmetry-constrained structural solution

Low-energy electron-diffraction (LEED) patterns of the Au(111)(2√3×3)rect.-butylthiolate surface phase (a structure also seen in longer alkane chain thiolate self-assembled monolayers) show missing diffracted beams characteristic of glide symmetry, but do not show the larger set of missing beams found in surface x-ray diffraction (SXRD). The difference can be attributed to the greatly enhanced role of multiple scattering in LEED, but the combination of symmetry constraints placed on possible structural models by the observed SXRD and LEED beam extinctions greatly reduces the number of possible structural models. Only three such models are identified, one of which is clearly incompatible with other published experimental data. The relative merits of the remaining models, both involving Au adatom-thiolate moieties, are discussed in the light of the results of previous experimental studies

Use of an index to reflect the aggregate burden of long-term exposure to criteria air pollutants in the United States.

Air pollution control in the United States for five common pollutants--particulate matter, ground-level ozone, sulfur dioxide, nitrogen dioxide, and carbon monoxide--is based partly on the attainment of ambient air quality standards that represent a level of air pollution regarded as safe. Regulatory and health agencies often focus on whether standards for short periods are attained; the number of days that standards are exceeded is used to track progress. Efforts to explain air pollution to the public often incorporate an air quality index that represents daily concentrations of pollutants. While effects of short-term exposures have been emphasized, research shows that long-term exposures to lower concentrations of air pollutants can also result in adverse health effects. We developed an aggregate index that represents long-term exposure to these pollutants, using 1995 monitoring data for metropolitan areas obtained from the U.S. Environmental Protection Agency's Aerometric Information Retrieval System. We compared the ranking of metropolitan areas under the proposed aggregate index with the ranking of areas by the number of days that short-term standards were exceeded. The geographic areas with the highest burden of long-term exposures are not, in all cases, the same as those with the most days that exceeded a short-term standard. We believe that an aggregate index of long-term air pollution offers an informative addition to the principal approaches currently used to describe air pollution exposures; further work on an aggregate index representing long-term exposure to air pollutants is warranted

Photoelectron diffraction: from phenomenological demonstration to practical tool

The potential of photoelectron diffraction—exploiting the coherent interference of directly-emitted and elastically scattered components of the photoelectron wavefield emitted from a core level of a surface atom to obtain structural information—was first appreciated in the 1970s. The first demonstrations of the effect were published towards the end of that decade, but the method has now entered the mainstream armoury of surface structure determination. This short review has two objectives: First, to outline the way that the idea emerged and the way this evolved in my own collaboration with Neville Smith and his colleagues at Bell Labs in the early years: Second, to provide some insight into the current state-of-the art in application of (scanned-energy mode) photoelectron diffraction to address two key issue in quantitative surface structure determination, namely, complexity and precision. In this regard a particularly powerful aspect of photoelectron diffraction is its elemental and chemical-state specificity

The local adsorption site of methylthiolate on Au(1 1 1): Bridge or atop?

Measurements of the local adsorption geometry of the S head-group atom in the Au(1 1 1)(√3 × √3)R30°–CH3S surface have been made using normal incidence X-ray standing waves (NIXSW) and S 1s scanned-energy mode photoelectron diffraction on the same surface preparations. The results confirm that the local adsorption site is atop an Au atom in a bulk-continuation site with a S–Au bondlength of 2.42 ± 0.02 Å, and that there can be no significant fraction of coadsorbed bridging species as recently proposed in a combined molecular dynamics/experimental study by Mazzarello et al. [R. Mazzarello, A. Cossaro, A. Verdini, R. Rousseau, L. Casalis, M.F. Danisman, L. Floreano, S. Scandolo, A. Morgante, G. Scoles, Phys. Rev. Lett. 98 (2007) 016102]. The results do not, however, clearly distinguish the different local reconstruction (adatom) models proposed for this surface

Local methylthiolate adsorption geometry on Au(111) from photoemission core-level shifts

The local adsorption structure of methylthiolate in the ordered Au(111)-(√3×√3)R30° phase has been investigated using core-level-shift measurements of the surface and bulk components of the Au 4f7/2 photoelectron binding energy. The amplitude ratio of the core-level-shift components associated with surface Au atoms that are, and are not, bonded to the thiolate is found to be compatible only with the previously proposed Au-adatom-monothiolate moiety in which the thiolate is bonded atop Au adatoms in hollow sites, and not on an unreconstructed surface, or in Au-adatom-dithiolate species

Avenues of future research in homotransplantation of the liver with particular reference to hepatic supportive procedures, antilymphocyte serum, and tissue typing

Three general areas of research which bear on the developing field of liver transplantation are reviewed. These are: (1) the prospects of obtaining better immunosuppression with particular reference to heterologous antilymphocyte serum; (2) the possible use of antigen matching technics as an advanced indicator of donorrecipient histocompatibility; (3) a simlified system of extracorporeal transplntation designed to provide teporary hepatic support. © 1966

The local adsorption structure of benzene on Si(001)-(2 × 1): a photoelectron diffraction investigation

Scanned-energy mode C 1s photoelectron diffraction has been used to investigate the local adsorption geometry of benzene on Si(001) at saturation coverage and room temperature. The results show that two different local bonding geometries coexist, namely the 'standard butterfly' (SB) and 'tilted bridge' (TB) forms, with a composition of 58 ± 29% of the SB species. Detailed structural parameter values are presented for both species including Si–C bond lengths. On the basis of published measurements of the rate of conversion of the SB to the TB form on this surface, we estimate that the timescale of our experiment is sufficient for achieving equilibrium, and in this case our results indicate that the difference in the Gibbs free energy of adsorption, ΔG(TB)−ΔG(SB), is in the range −0.023 to +0.049 eV. We suggest, however, that the relative concentration of the two species may also be influenced by a combination of steric effects influencing the kinetics, and a sensitivity of the adsorption energies of the adsorbed SB and TB forms to the nature of the surrounding benzene molecules

Renormalisation-theoretic analysis of non-equilibrium phase transitions II: The effect of perturbations on rate coefficients in the Becker-Doring equations

We study in detail the application of renormalisation theory to models of cluster aggregation and fragmentation of relevance to nucleation and growth processes. In particular, we investigate the Becker-Doring (BD) equations, originally formulated to describe and analyse non-equilibrium phase transitions, but more recently generalised to describe a wide range of physicochemical problems. We consider here rate coefficients which depend on the cluster size in a power-law fashion, but now perturbed by small amplitude random noise. Power-law rate coefficients arise naturally in the theory of surface-controlled nucleation and growth processes. The noisy perturbations on these rates reflect the effect of microscopic variations in such mean-field coefficients, thermal fluctuations and/or experimental uncertainties. In the present paper we generalise our earlier work that identified the nine classes into which all dynamical behaviour must fall by investigating how random perturbations of the rate coefficients influence the steady-state and kinetic behaviour of the coarse-grained, renormalised system. We are hence able to confirm the existence of a set of up to nine universality classes for such BD systems.Comment: 30 pages, to appear in J Phys A Math Ge

Renormalisation-theoretic analysis of non-equilibrium phase transitions I: The Becker-Doring equations with power law rate coefficients

We study in detail the application of renormalisation theory to models of cluster aggregation and fragmentation of relevance to nucleation and growth processes. We investigate the Becker-Dorging equations, originally formulated to describe and analyse non-equilibrium phase transitions, and more recently generalised to describe a wide range of physicochemical problems. In the present paper we analyse how the systematic coarse-graining renormalisation of the \BD system of equations affects the aggregation and fragmentation rate coefficients. We consider the case of power-law size-dependent cluster rate coefficients which we show lead to only three classes of system that require analysis: coagulation-dominated systems, fragmentation-dominated systems and those where coagulation and fragmentation are exactly balanced. We analyse the late-time asymptotics associated with each class.Comment: 18 pages, to appear in J Phys A Math Ge