Energy-dependent cancellation of diffraction spots due to surface roughening

The low-energy electron diffraction (LEED) pattern of the step-kinked Pt{531} surface at 200 K shows energy-dependent cancellation of diffraction spots over unusually large energy ranges, up to 100 eV. This cannot be reproduced theoretically when a flat surface geometry is assumed. A relatively simple model of roughening, however, involving 0.25 ML of vacancies and adatoms leads to very good agreement with the experiment. The cancellation of intensities within a very narrow range of adatom or vacancy coverages is caused by the interference of electrons emerging from different heights but similar local environments. This is a rare example where the energy dependence of integrated LEED spot intensities is dramatically affected by the long-range arrangement of atoms.

Suprathermal electron evolution in a Parker spiral magnetic field

Suprathermal electrons (>70 eV) form a small fraction of the total solar wind electron density but serve as valuable tracers of heliospheric magnetic field topology. Their usefulness as tracers of magnetic loops with both feet rooted on the Sun, however, most likely fades as the loops expand beyond some distance owing to scattering. As a first step toward quantifying that distance, we construct an observationally constrained model for the evolution of the suprathermal electron pitch-angle distributions on open field lines. We begin with a near-Sun isotropic distribution moving antisunward along a Parker spiral magnetic field while conserving magnetic moment, resulting in a field-aligned strahl within a few solar radii. Past this point, the distribution undergoes little evolution with heliocentric distance. We then add constant (with heliocentric distance, energy, and pitch angle) ad-hoc pitch-angle scattering. Close to the Sun, pitch-angle focusing still dominates, again resulting in a narrow strahl. Farther from the Sun, however, pitch-angle scattering dominates because focusing is effectively weakened by the increasing angle between the magnetic field direction and intensity gradient, a result of the spiral field. We determine the amount of scattering required to match Ulysses observations of strahl width in the fast solar wind, providing an important tool for inferring the large-scale properties and topologies of field lines in the interplanetary medium. Although the pitch-angle scattering term is independent of energy, time-of-flight effects in the spiral geometry result in an energy dependence of the strahl width that is in the observed sense although weaker in magnitude.

Understanding electron heat flux signatures in the solar wind

Suprathermal electrons (E > 80 eV) carry heat flux away from the Sun. Processes controlling the heat flux are not well understood. To gain insight into these processes, we model heat flux as a linear dependence on two independent parameters: electron number flux and electron pitch angle anisotropy. Pitch angle anisotropy is further modeled as a linear dependence on two solar wind components: magnetic field strength and plasma density. These components show no correlation with number flux, reinforcing its independence from pitch angle anisotropy. Multiple linear regression applied to 2 years of Wind data shows good correspondence between modeled and observed heat flux and anisotropy. The results suggest that the interplay of solar wind parameters and electron number flux results in distinctive heat flux dropouts at heliospheric features like plasma sheets but that these parameters continuously modify heat flux. This is inconsistent with magnetic disconnection as the primary cause of heat flux dropouts. Analysis of fast and slow solar wind regimes separately shows that electron number flux and pitch angle anisotropy are equally correlated with heat flux in slow wind but that number flux is the dominant correlative in fast wind. Also, magnetic field strength correlates better with pitch angle anisotropy in slow wind than in fast wind. The energy dependence of the model fits suggests different scattering processes in fast and slow wind.

Complete Experimental Structure Determination of the p(3x2)pg Phase of Glycine on Cu{110}

We present a quantitative low energy electron diffraction (LEED) surface-crystallograpic study of the complete adsorption geometry of glycine adsorbed on Cu{110} in the ordered p(3×2) phase. The glycine molecules form bonds to the surface through the N atoms of the amino group and the two O atoms of the de-protonated carboxylate group, each with separate Cu atoms such that every Cu atom in the first layer is involved in a bond. Laterally, N atoms are nearest to the atop site (displacement 0.41 Å). The O atoms are asymmetrically displaced from the atop site by 0.54 Å and 1.18 Å with two very different O-Cu bond lengths of 1.93 Å and 2.18 Å. The atom positions of the upper-most Cu layers show small relaxations within 0.07 Å of the bulk-truncated surface geometry. The unit cell of the adsorbate layer consists of two glycine molecules, which are related by a glide-line symmetry operation. This study clearly shows that a significant coverage of adsorbate structures without this glide-line symmetry must be rejected, both on the grounds of the energy dependence of the spot intensities (LEED-IV curves) and of systematic absences in the LEED pattern.

Further investigations of the quartz optically stimulated luminescence components using linear modulation

The optically stimulated luminescence (OSL) from quartz is known to be the sum of several components with different rates of charge loss, originating from different trap types. The OSL components are clearly distinguished using the linear modulation (LM OSL) technique. A variety of pre-treatment and measurement conditions have been used on sedimentary samples in conjunction with linearly modulated optical stimulation to study in detail the behaviour of the OSL components of quartz. Single aliquots of different quartz samples have been found to contain typically five or six common LM OSL components when stimulated at View the MathML source. The components have been parameterised in terms of thermal stability (i.e. E and s), photoionisation cross-section energy dependence and dose response. The results of studies concerning applications of component-resolved LM OSL measurements on quartz are also presented. These include the detection of partial bleaching in young samples, use of ‘stepped wavelength’ stimulation to observe OSL from single components and attempts to extend the age range of quartz OSL dating.

Carbon suboxide: the vibrational dependence of the v7 bending potential function

Data on the vibrational energy levels and rotational constants of carbon suboxide for the low-wavenumber bending mode ν7 are reviewed, in the ground-state manifold, and in the ν2-, ν3-, ν4-, and ν2 + ν4-state manifolds. Following the procedure developed by Duckett, Mills, and Robiette [J. Mol. Spectrosc. 63, 249 (1976)] the data have been inverted to give the effective bending potential in ν7 for each of these five states. Values are obtained for various other parameters in the effective vibration-rotation Hamiltonian. The potential and rotational constants in ν2 + ν4 are given to a close approximation by linear extrapolation from the ground state through the ν2 and ν4 states.

An investigation of the germylene addition reaction, GeH2+C2H2: Time-resolved gas-phase kinetic studies and quantum chemical calculations of the reaction energy surface

Time resolved studies of germylene, GeH2, generated by laser flash photolysis of 3,4-dimethylgermacyclopentene-3, have been carried out to obtain rate constants for its bimolecular reaction with acetylene, C2H2. The reaction was studied in the gas-phase over the pressure range 1-100 Tort, with SF6 as bath gas, at 5 temperatures in the range 297-553 K. The reaction showed a very slight pressure dependence at higher temperatures. The high pressure rate constants (obtained by extrapolation at the three higher temperatures) gave the Arrhenius equation: log(k(infinity)/cm(3) molecule(-1) s(-1)) (-10.94 +/- 0.05) + (6.10 +/- 0.36 kJ mol(-1))/RTln10. These Arrhenius parameters are consistent with a fast reaction occurring at approximately 30% of the collision rate at 298 K. Quantum chemical calculations (both DFT and ab initio G2//B3LYP and G2//QCISD) of the GeC2H4 potential energy surface (PES), show that GeH2 + C2H2 react initially to form germirene which can isomerise to vinylgermylene with a relatively low barrier. RRKM modelling, based on a loose association transition state, but assuming vinylgermylene is the end product (used in combination with a weak collisional deactivation model) predicts a strong pressure dependence using the calculated energies, in conflict with the experimental evidence. The detailed GeC2H4 PES shows considerable complexity with ten other accessible stable minima (B3LYP level), the three most stable of which are all germylenes. Routes through this complex surface were examined in detail. The only product combination which appears capable of satisfying the (P-3) + C2H4.C2H4 was confirmed as a product by GC observed lack of a strong pressure dependence is Ge(P-3) + C2H4. C2H4 was confirmed as a product by GC analysis. Although the formation of these products are shown to be possible by singlet-triplet curve crossing during dissociation of 1-germiranylidene (1-germacyclopropylidene), it seems more likely (on thermochernical grounds) that the triplet biradical, (GeCH2CH2.)-Ge-., is the immediate product precursor. Comparisons are made with the reaction of SiH2 with C2H2.

The gas-phase reaction between silylene and 2-butyne: kinetics, isotope studies, pressure dependence studies and quantum chemical calculations

Time-resolved kinetic studies of the reactions of silylene, SiH2, and dideutero-silylene, SiD2, generated by laser. ash photolysis of phenylsilane and phenylsilane-d(3), respectively, have been carried out to obtain rate coefficients for their bimolecular reactions with 2-butyne, CH3C CCH3. The reactions were studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas at five temperatures in the range 294-612 K. The second-order rate coefficients, obtained by extrapolation to the high pressure limits at each temperature, fitted the Arrhenius equations where the error limits are single standard deviations: log(k(H)(infinity)/cm(3) molecule(-1) s(-1)) = (-9.67 +/- 0.04) + (1.71 +/- 0.33) kJ mol(-1)/RTln10 log(k(D)(infinity)/cm(3) molecule(-1) s(-1)) = (-9.65 +/- 0.01) + (1.92 +/- 0.13) kJ mol(-1)/RTln10 Additionally, pressure-dependent rate coefficients for the reaction of SiH2 with 2-butyne in the presence of He (1-100 Torr) were obtained at 301, 429 and 613 K. Quantum chemical (ab initio) calculations of the SiC4H8 reaction system at the G3 level support the formation of 2,3-dimethylsilirene [cyclo-SiH2C(CH3)=C(CH3)-] as the sole end product. However, reversible formation of 2,3-dimethylvinylsilylene [CH3CH=C(CH3)SiH] is also an important process. The calculations also indicate the probable involvement of several other intermediates, and possible products. RRKM calculations are in reasonable agreement with the pressure dependences at an enthalpy value for 2,3-dimethylsilirene fairly close to that suggested by the ab initio calculations. The experimental isotope effects deviate significantly from those predicted by RRKM theory. The differences can be explained by an isotopic scrambling mechanism, involving H - D exchange between the hydrogens of the methyl groups and the D-atoms in the ring in 2,3-dimethylsilirene-1,1-d(2). A detailed mechanism involving several intermediate species, which is consistent with the G3 energy surface, is proposed to account for this.

Energy overview of Botswana: generation and consumption

Botswana has a basic need to explore its energy concept, this being its energy sources, generation and percentage of the population with access to electricity. At present, Botswana generates electricity from coal, which supplies about 29% (on average) of the country’s demand. The other 71% is imported mainly from South Africa (Eskom). Consequently, the dependence of Botswana on imports posses threats to the security of its energy supply. As a result, there is the need to understand the bases for a possible generation expansion that would substantiate existing documentation. In view of this need, this study investigates the existing energy sources as well as energy consumption and production levels in Botswana. The study would be further developed by making projections of the energy demand up until the year 2020. The key techniques that were used include; literature review, questionnaire survey and an empirical study. The results presented indicated that, current dependable operation capacity (i.e. 100MW) should be increased to 2,595 MW or more assuming 85% plant efficiency. This would then be able to meet the growing demand for energy use. In addition, the installed capacity would be able to support commercial and mining activities for the growth of the economy.

Numerical modelling of the energy and water cycle of the Baltic Sea

This paper will introduce the Baltex research programme and summarize associated numerical modelling work which has been undertaken during the last five years. The research has broadly managed to clarify the main mechanisms determining the water and energy cycle in the Baltic region, such as the strong dependence upon the large scale atmospheric circulation. It has further been shown that the Baltic Sea has a positive water balance, albeit with large interannual variations. The focus on the modelling studies has been the use of limited area models at ultra-high resolution driven by boundary conditions from global models or from reanalysis data sets. The programme has further initiated a comprehensive integration of atmospheric, land surface and hydrological modelling incorporating snow, sea ice and special lake models. Other aspects of the programme include process studies such as the role of deep convection, air sea interaction and the handling of land surface moisture. Studies have also been undertaken to investigate synoptic and sub-synoptic events over the Baltic region, thus exploring the role of transient weather systems for the hydrological cycle. A special aspect has been the strong interests and commitments of the meteorological and hydrological services because of the potentially large societal interests of operational applications of the research. As a result of this interests special attention has been put on data-assimilation aspects and the use of new types of data such as SSM/I, GPS-measurements and digital radar. A series of high resolution data sets are being produced. One of those, a 1/6 degree daily precipitation climatology for the years 1996–1999, is such a unique contribution. The specific research achievements to be presented in this volume of Meteorology and Atmospheric Physics is the result of a cooperative venture between 11 European research groups supported under the EU-Framework programmes.

Nonlinear saturation of baroclinic instability: part III: bounds on the energy

Rigorous upper bounds are derived on the saturation amplitude of baroclinic instability in the two-layer model. The bounds apply to the eddy energy and are obtained by appealing to a finite amplitude conservation law for the disturbance pseudoenergy. These bounds are to be distinguished from those derived in Part I of this study, which employed a pseudomomentum conservation law and provided bounds on the eddy potential enstrophy. The bounds apply to conservative (inviscid, unforced) flow, as well as to forced-dissipative flow when the dissipation is proportional to the potential vorticity. Bounds on the eddy energy are worked out for a general class of unstable westerly jets. In the special case of the Phillips model of baroclinic instability, and in the limit of infinitesimal initial eddy amplitude, the bound states that the eddy energy cannot exceed ϵβ2/6F where ϵ = (U − Ucrit)/Ucrit is the relative supercriticality. This bound captures the essential dynamical scalings (i.e., the dependence on ϵ, β, and F) of the saturation amplitudes predicted by weakly nonlinear theory, as well as exhibiting remarkable quantitative agreement with those predictions, and is also consistent with heuristic baroclinic adjustment estimates.

The dependence of southern ocean meridional overturning on wind stress

An eddy-resolving numerical model of a zonal flow, meant to resemble the Antarctic Circumpolar Current, is described and analyzed using the framework of J. Marshall and T. Radko. In addition to wind and buoyancy forcing at the surface, the model contains a sponge layer at the northern boundary that permits a residual meridional overturning circulation (MOC) to exist at depth. The strength of the residual MOC is diagnosed for different strengths of surface wind stress. It is found that the eddy circulation largely compensates for the changes in Ekman circulation. The extent of the compensation and thus the sensitivity of the MOC to the winds depend on the surface boundary condition. A fixed-heat-flux surface boundary severely limits the ability of the MOC to change. An interactive heat flux leads to greater sensitivity. To explain the MOC sensitivity to the wind strength under the interactive heat flux, transformed Eulerian-mean theory is applied, in which the eddy diffusivity plays a central role in determining the eddy response. A scaling theory for the eddy diffusivity, based on the mechanical energy balance, is developed and tested; the average magnitude of the diffusivity is found to be proportional to the square root of the wind stress. The MOC sensitivity to the winds based on this scaling is compared with the true sensitivity diagnosed from the experiments.

Energy supply, consumption and access dynamics in Botswana

The growing dependence on electricity for economic growth in all countries prompts the need to manage current resources for future sustainability. In today’s world, greater emphasis is placed on energy conservation for energy security and for the development of every economy. However, for some countries understanding the basic drivers to such achievements is farfetched. The research presented in this paper investigates the electricity generation and access potential for Botswana. In addition detailed documentation and 13 years energy consumption and generation trends are investigated. Using questionnaires and empirical studies the energy demand for the entire nation was estimated. From the research it was established that current energy generation trends account for 38- 39% of the country’s population with access to electricity. Considering the percentage rate of sector energy demand, the proposed total installed capacity of 1332 MW, would not meet the country's energy demand at 100% access. The likely consequence of the lack of adequate supply would cumulate to significant increase of imports and/or load shedding to meet demand.

Surface chemistry of alanine on Cu{111}: Adsorption geometry and temperature dependence

Adsorption of l-alanine on the Cu{111} single crystal surface was investigated as a model system for interactions between small chiral modifier molecules and close-packed metal surfaces. Synchrotron-based X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy are used to determine the chemical state, bond coordination and out-of-plane orientation of the molecule on the surface. Alanine adsorbs in its anionic form at room temperature, whilst at low temperature the overlayer consists of anionic and zwitterionic molecules. NEXAFS spectra exhibit a strong angular dependence of the π ⁎ resonance associated with the carboxylate group, which allows determining the tilt angle of this group with respect to the surface plane (48° ± 2°) at room temperature. Low-energy electron diffraction (LEED) shows a p(2√13x2√13)R13° superstructure with only one domain, which breaks the mirror symmetry of the substrate and, thus, induces global chirality to the surface. Temperature-programmed XPS (TP-XPS) and temperature-programmed desorption (TPD) experiments indicate that the zwitterionic form converts into the anionic species (alaninate) at 293 K. The latter desorbs/decomposes between 435 K and 445 K.

Extended cusp-like regions and their dependence on the Polar orbit, seasonal variations, and interplanetary conditions

Extended cusp-like regions (ECRs) are surveyed, as observed by the Magnetospheric Ion Composition Sensor (MICS) of the Charge and Mass Magnetospheric Ion Composition Experiment (CAMMICE) instrument aboard Polar between 1996 and 1999. The first of these ECR events was observed on 29 May 1996, an event widely discussed in the literature and initially thought to be caused by tail lobe reconnection due to the coinciding prolonged interval of strong northward IMF. ECRs are characterized here by intense fluxes of magnetosheath-like ions in the energy-per-charge range of _1 to 10 keV e_1. We investigate the concurrence of ECRs with intervals of prolonged (lasting longer than 1 and 3 hours) orientations of the IMF vector and high solar wind dynamic pressure (PSW). Also investigated is the opposite concurrence, i.e., of the IMF and high PSW with ECRs. (Note that these surveys are asking distinctly different questions.) The former survey indicates that ECRs have no overall preference for any orientation of the IMF. However, the latter survey reveals that during northward IMF, particularly when accompanied by high PSW, ECRs are more likely. We also test for orbital and seasonal effects revealing that Polar has to be in a particular region to observe ECRs and that they occur more frequently around late spring. These results indicate that ECRs have three distinct causes and so can relate to extended intervals in (1) the cusp on open field lines, (2) the magnetosheath, and (3) the magnetopause indentation at the cusp, with the latter allowing magnetosheath plasma to approach close to the Earth without entering the magnetosphere.