Quantification of boundary definition using pulsed terahertz radiation for wedged geometries

The interaction of a terahertz beam with a sample containing a material boundary across the profile of the terahertz beam produces characteristic spectroscopic detail. A full vectorial model is presented to quantify boundary definition for a series of wedged geometries. As a result of this work, using simple geometric forms, we wish to be able to extend these ideas to characterize boundaries in more irregular samples, impacting most application areas of pulsed terahertz radiation.

A numerical scheme for two-dimensional, open channel flows with non-rectangular geometries

An algorithm based on flux difference splitting is presented for the solution of two-dimensional, open channel flows. A transformation maps a non-rectangular, physical domain into a rectangular one. The governing equations are then the shallow water equations, including terms of slope and friction, in a generalized coordinate system. A regular mesh on a rectangular computational domain can then be employed. The resulting scheme has good jump capturing properties and the advantage of using boundary/body-fitted meshes. The scheme is applied to a problem of flow in a river whose geometry induces a region of supercritical flow.

The surface geometries of the medium and high coverage carbon monoxide structures c(2 × 4)–(2CO) and p(root7- x root7)R19°–(4CO) structure

The surface geometries of the p (root7- x root7)R19degrees-(4CO) and c(2 x 4)-(2CO) layers on Ni {111} and the clean Ni {111} surface were determined by low energy electron diffraction structure analysis. For the clean surface small but significant contractions of d(12) and d(23) (both 2.02 Angstrom) were found with respect to the bulk interlayer distance (2.03 Angstrom). In the c(2 x 4)-(2CO) structure these distances are expanded, with values of d(12) = 2.08 Angstrom and d(23) = 2.06 Angstrom and buckling of 0.08 and 0.02 Angstrom, respectively, in the first and second layer. CO resides near hcp and fcc hollow sites with relatively large lateral shifts away from the ideal positions leading to unequal C-Ni bond lengths between 1.76 and 1.99 Angstrom. For the p(root7- x root7-)R19'-(4CO) layer two best fit geometries were found, which agree in most of their atomic positions, except for one out of four CO molecules, which is either near atop or between bridge and atop. The remaining three molecules reside near hcp and fcc sites, again with large lateral deviations from their ideal positions. The average C Ni bond length for these molecules is, however, the same as for CO on hollow sites at low coverage. The average CNi bond length at hollow sites, the interlayer distances, and buckling in the first Ni layer are similar to the c(2 x 4)(2CO) geometry, only the buckling in the second layer (0.08 Angstrom) is significantly larger. Lateral and vertical shifts of the Ni atoms in the first layer lead to unsymmetric environments for the CO molecules, which can be regarded as an imprint of the chiral p(root7- x root7-)R19degrees lattice geometry onto the substrate.

The interaction of flexural-gravity waves with periodic geometries

A periodic structure of finite extent is embedded within an otherwise uniform two-dimensional system consisting of finite-depth fluid covered by a thin elastic plate. An incident harmonic flexural-gravity wave is scattered by the structure. By using an approximation to the corresponding linearised boundary value problem that is based on a slowly varying structure in conjunction with a transfer matrix formulation, a method is developed that generates the whole solution from that for just one cycle of the structure, providing both computational savings and insight into the scattering process. Numerical results show that variations in the plate produce strong resonances about the ‘Bragg frequencies’ for relatively few periods. We find that certain geometrical variations in the plate generate these resonances above the Bragg value, whereas other geometries produce the resonance below the Bragg value. The familiar resonances due to periodic bed undulations tend to be damped by the plate.

The diabatic contour advective semi-Lagrangian model

This article describes a novel algorithmic development extending the contour advective semi-Lagrangian model to include nonconservative effects. The Lagrangian contour representation of finescale tracer fields, such as potential vorticity, allows for conservative, nondiffusive treatment of sharp gradients allowing very high numerical Reynolds numbers. It has been widely employed in accurate geostrophic turbulence and tracer advection simulations. In the present, diabatic version of the model the constraint of conservative dynamics is overcome by including a parallel Eulerian field that absorbs the nonconservative ( diabatic) tendencies. The diabatic buildup in this Eulerian field is limited through regular, controlled transfers of this field to the contour representation. This transfer is done with a fast newly developed contouring algorithm. This model has been implemented for several idealized geometries. In this paper a single-layer doubly periodic geometry is used to demonstrate the validity of the model. The present model converges faster than the analogous semi-Lagrangian models at increased resolutions. At the same nominal spatial resolution the new model is 40 times faster than the analogous semi-Lagrangian model. Results of an orographically forced idealized storm track show nontrivial dependency of storm-track statistics on resolution and on the numerical model employed. If this result is more generally applicable, this may have important consequences for future high-resolution climate modeling.

General relationships between pressure, weight, and mass of a hydrostatic fluid

In curved geometries the hydrostatic pressure in a fluid does not equal the weight per unit area of the fluid above it. General weight–pressure and mass–pressure relationships for hydrostatic fluids in any geometry are derived. As an example of the mass–pressure relationship, we find a geometric reduction in surface pressure as large as 5 mbar on Earth and 39 mbar on Titan. We also present a thermodynamic interpretation of the geometric correction which, as a corollary, provides an independent proof of the hydrostatic relationship for general geometries.

Wind-tunnel modelling of dispersion from a scalar area source in urban-like roughness

A wind-tunnel study was conducted to investigate ventilation of scalars from urban-like geometries at neighbourhood scale by exploring two different geometries a uniform height roughness and a non-uniform height roughness, both with an equal plan and frontal density of λ p = λ f = 25%. In both configurations a sub-unit of the idealized urban surface was coated with a thin layer of naphthalene to represent area sources. The naphthalene sublimation method was used to measure directly total area-averaged transport of scalars out of the complex geometries. At the same time, naphthalene vapour concentrations controlled by the turbulent fluxes were detected using a fast Flame Ionisation Detection (FID) technique. This paper describes the novel use of a naphthalene coated surface as an area source in dispersion studies. Particular emphasis was also given to testing whether the concentration measurements were independent of Reynolds number. For low wind speeds, transfer from the naphthalene surface is determined by a combination of forced and natural convection. Compared with a propane point source release, a 25% higher free stream velocity was needed for the naphthalene area source to yield Reynolds-number-independent concentration fields. Ventilation transfer coefficients w T /U derived from the naphthalene sublimation method showed that, whilst there was enhanced vertical momentum exchange due to obstacle height variability, advection was reduced and dispersion from the source area was not enhanced. Thus, the height variability of a canopy is an important parameter when generalising urban dispersion. Fine resolution concentration measurements in the canopy showed the effect of height variability on dispersion at street scale. Rapid vertical transport in the wake of individual high-rise obstacles was found to generate elevated point-like sources. A Gaussian plume model was used to analyse differences in the downstream plumes. Intensified lateral and vertical plume spread and plume dilution with height was found for the non-uniform height roughness

Adsorption, orientation and thermal decomposition of copper(II) hexafluoroacetylacetonate on rutile TiO2(110)

We have investigated the adsorption and thermal decomposition of copper hexafluoroacetylacetonate (Cu-11(hfaC)(2)) on single crystal rutile TiO2(110). Low energy electron diffraction shows that room temperature saturation coverage of the Cu-II(hfac)(2) adsorbate forms an ordered (2 x 1) over-layer. X-ray and ultra-violet photoemission spectroscopy of the saturated surface were recorded as the sample was annealed in a sequential manner to reveal decomposition pathways. The results show that the molecule dissociatively adsorbs by detachment of one of the two ligands to form hfac and Cu-1(hfac) which chemisorb to the substrate at 298 K. These ligands only begin to decompose once the surface temperature exceeds 473 K where Cu core level shifts indicate metallisation. This reduction from Cu(I) to Cu(0) takes place in the absence of an external reducing agent and without disproportionation and is accompanied by the onset of decomposition of the hfac ligands. Finally, C K-edge near edge X-ray absorption fine structure experiments indicate that both the ligands adsorb aligned in the < 001 > direction and we propose a model in which the hfac ligands adsorb on the 5-fold coordinated Ti atoms and the Cu-1(hfac) moiety attaches to the bridging O atoms in a square planar geometry. The calculated tilt angle for these combined geometries is approximately 10 degrees to the surface normal.

How many facets are needed to represent the surface energy balance of an urban area?

We investigate the question of how many facets are needed to represent the energy balance of an urban area by developing simplified 3-, 2- and 1-facet versions of a 4-facet energy balance model of two-dimensional streets and buildings. The 3-facet model simplifies the 4-facet model by averaging over the canyon orientation, which results in similar net shortwave and longwave balances for both wall facets, but maintains the asymmetry in the heat fluxes within the street canyon. For the 2-facet model, on the assumption that the wall and road temperatures are equal, the road and wall facets can be combined mathematically into a single street-canyon facet with effective values of the heat transfer coefficient, albedo, emissivity and thermodynamic properties, without further approximation. The 1-facet model requires the additional assumption that the roof temperature is also equal to the road and wall temperatures. Idealised simulations show that the geometry and material properties of the walls and road lead to a large heat capacity of the combined street canyon, whereas the roof behaves like a flat surface with low heat capacity. This means that the magnitude of the diurnal temperature variation of the street-canyon facets are broadly similar and much smaller than the diurnal temperature variation of the roof facets. Consequently, the approximation that the street-canyon facets have similar temperatures is sound, and the road and walls can be combined into a single facet. The roof behaves very differently and a separate roof facet is required. Consequently, the 2-facet model performs similarly to the 4-facet model, while the 1-facet model does not. The models are compared with previously published observations collected in Mexico City. Although the 3- and 2-facet models perform better than the 1-facet model, the present models are unable to represent the phase of the sensible heat flux. This result is consistent with previous model comparisons, and we argue that this feature of the data cannot be produced by a single column model. We conclude that a 2-facet model is necessary, and for numerical weather prediction sufficient, to model an urban surface, and that this conclusion is robust and therefore applicable to more general geometries.

Rational modification of the hierarchy of intermolecular interactions in molecular crystal structures by using tunable halogen bonds

A family of 16 isomolecular salts (3-XpyH)(2)[MX'(4)] (3-XpyH=3-halopyridinium; M=Co, Zn; X=(F), Cl, Br, (I); X'=Cl, Br, I) each containing rigid organic cations and tetrahedral halometallate anions has been prepared and characterized by X-ray single crystal and/or powder diffraction. Their crystal structures reflect the competition and cooperation between non-covalent interactions: N-H center dot center dot center dot X'-M hydrogen bonds, C-X center dot center dot center dot X'-M halogen bonds and pi-pi stacking. The latter are essentially unchanged in strength across the series, but both halogen bonds and hydrogen bonds are modified in strength upon changing the halogens involved. Changing the organic halogen (X) from F to I strengthens the C-X center dot center dot center dot X'-M halogen bonds, whereas an analogous change of the inorganic halogen (X') weakens both halogen bonds and N-H center dot center dot center dot X'-M hydrogen bonds. By so tuning the strength of the putative halogen bonds from repulsive to weak to moderately strong attractive interactions, the hierarchy of the interactions has been modified rationally leading to systematic changes in crystal packing. Three classes of crystal structure are obtained. In type A (C-F center dot center dot center dot X'-M) halogen bonds are absent. The structure is directed by N-H center dot center dot center dot X'-M hydrogen bonds and pi-stacking interactions. In type B structures, involving small organic halogens (X) and large inorganic halogens (X'), long (weak) C-X center dot center dot center dot X'-M interactions are observed with type I halogen-halogen interaction geometries (C-X center dot center dot center dot X' approximate to X center dot center dot center dot X'-M approximate to 155 degrees), but hydrogen bonds still dominate. Thus, minor but quite significant perturbations from the type A structure arise. In type C, involving larger organic halogens (X) and smaller inorganic halogens (X'), stronger halogen bonds are formed with a type II halogen-halogen interaction geometry (C-X center dot center dot center dot X' approximate to 180 degrees; X center dot center dot center dot X'-M approximate to 110 degrees) that is electrostatically attractive. The halogen bonds play a major role alongside hydrogen bonds in directing the type C structures, which as a result are quite different from type A and B.

A field study of factors influencing the concentrations of a traffic-related pollutant in the vicinity of a complex urban junction

The paper describes a field study focused on the dispersion of a traffic-related pollutant within an area close to a busy intersection between two street canyons in Central London. Simultaneous measurements of airflow, traffic flow and carbon monoxide concentrations ([CO]) are used to explore the causes of spatial variability in [CO] over a full range of background wind directions. Depending on the roof-top wind direction, evidence of both flow channelling and recirculation regimes were identified from data collected within the main canyon and the intersection. However, at the intersection, the merging of channelled flows from the canyons increased the flow complexity and turbulence intensity. These features, coupled with the close proximity of nearby queuing traffic in several directions, led to the highest overall time-average measured [CO] occurring at the intersection. Within the main street canyon, the data supported the presence of a helical flow regime for oblique roof-top flows, leading to increased [CO] on the canyon leeward side. Predominant wind directions led to some locations having significantly higher diurnal average [CO] due to being mostly on the canyon leeward side during the study period. For all locations, small changes in the background wind direction could cause large changes in the in-street mean wind angle and local turbulence intensity, implying that dispersion mechanisms would be highly sensitive to small changes in above roof flows. During peak traffic flow periods, concentrations within parallel side streets were approximately four times lower than within the main canyon and intersection which has implications for controlling personal exposure. Overall, the results illustrate that pollutant concentrations can be highly spatially variable over even short distances within complex urban geometries, and that synoptic wind patterns, traffic queue location and building topologies all play a role in determining where pollutant hot spots occur.

Acoustic and petrophysical relationships in low-shale sandstone reservoir rocks

This paper describes the measurements of the acoustic and petrophysical properties of two suites of low-shale sandstone samples from North Sea hydrocarbon reservoirs, under simulated reservoir conditions. The acoustic velocities and quality factors of the samples, saturated with different pore fluids (brine, dead oil and kerosene), were measured at a frequency of about 0.8 MHz and over a range of pressures from 5 MPa to 40 MPa. The compressional-wave velocity is strongly correlated with the shear-wave velocity in this suite of rocks. The ratio V-P/V-S varies significantly with change of both pore-fluid type and differential pressure, confirming the usefulness of this parameter for seismic monitoring of producing reservoirs. The results of quality factor measurements were compared with predictions from Biot-flow and squirt-flow loss mechanisms. The results suggested that the dominating loss in these samples is due to squirt-flow of fluid between the pores of various geometries. The contribution of the Biot-flow loss mechanism to the total loss is negligible. The compressional-wave quality factor was shown to be inversely correlated with rock permeability, suggesting the possibility of using attenuation as a permeability indicator tool in low-shale, high-porosity sandstone reservoirs.

Ab initio and tight-binding calculations of noncollinear magnetism in manganese clusters

Combining ab initio and tight-binding calculations, we have studied the noncollinear magnetism in manganese clusters. The oscillations in the per-atom moments observed experimentally are reproduced theoretically. The tendency of antiferromagnetic coupling between near neighbors leads to noncollinear coupling between atoms within the clusters. For clusters containing 12, 13, 15, 19, and 23 atoms, the geometrical structures were optimized from ab initio calculations with collinear coupled spin moments among different atomic sites. For larger clusters such as Mn-36 and Mn-55, the geometries are taken as portions of an fcc structure. Although the local atomic moments have high values close to 4 mu(B), the net moments lie in the range of 0.4-1.2 mu(B)/atom. Taking the noncollinear coupling into account brings the calculated magnetic moments much closer to the experimental results.

Evaluation of the S(T) assimilation method with the Argo dataset

Recent observations from the Argo dataset of temperature and salinity profiles are used to evaluate a series of 3-year data assimilation experiments in a global ice–ocean general circulation model. The experiments are designed to evaluate a new data assimilation system whereby salinity is assimilated along isotherms, S(T ). In addition, the role of a balancing salinity increment to maintain water mass properties is investigated. This balancing increment is found to effectively prevent spurious mixing in tropical regions induced by univariate temperature assimilation, allowing the correction of isotherm geometries without adversely influencing temperature–salinity relationships. In addition, the balancing increment is able to correct a fresh bias associated with a weak subtropical gyre in the North Atlantic using only temperature observations. The S(T ) assimilation method is found to provide an important improvement over conventional depth level assimilation, with lower root-mean-squared forecast errors over the upper 500 m in the tropical Atlantic and Pacific Oceans. An additional set of experiments is performed whereby Argo data are withheld and used for independent evaluation. The most significant improvements from Argo assimilation are found in less well-observed regions (Indian, South Atlantic and South Pacific Oceans). When Argo salinity data are assimilated in addition to temperature, improvements to modelled temperature fields are obtained due to corrections to model density gradients and the resulting circulation. It is found that observations from the Argo array provide an invaluable tool for both correcting modelled water mass properties through data assimilation and for evaluating the assimilation methods themselves.