Exploring the free energy surfaces of clusters using reconnaissance metadynamics

A new approach is proposed for exploring the low-energy structures of small to medium-sized aggregates of atoms and molecules. This approach uses the recently proposed reconnaissance metadynamics method [G. A. Tribello, M. Ceriotti, and M. Parrinello. Proc. Natl. Acad. Sci. U.S.A. 107(41), 17509 (2010)] in tandem with collective variables that describe the average structure of the coordination sphere around the atoms/molecules. We demonstrate this method on both Lennard-Jones and water clusters and show how it is able to quickly find the global minimum in the potential energy surface, while exploring the finite temperature free energy surface. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3628676]

Surface energy and surface proton order of the ice Ih basal and prism surfaces

Density-functional theory (DFT) is used to examine the basal and prism surfaces of ice Ih. Similar surface energies are obtained for the two surfaces; however, in each case a strong dependence of the surface energy on surface proton order is identified. This dependence, which can be as much as 50% of the absolute surface energy, is significantly larger than the bulk dependence (< 1%) on proton order, suggesting that the thermodynamic ground state of the ice surface will remain proton ordered well above the bulk order-disorder temperature of about 72 K. On the basal surface this suggestion is supported by Monte Carlo simulations with an empirical potential and solution of a 2D Ising model with nearest neighbor interactions taken from DFT. Order parameters that define the surface energy of each surface in terms of nearest neighbor interactions between dangling OH bonds (those which point out of the surface into vacuum) have been identified and are discussed. Overall, these results suggest that proton order-disorder effects have a profound impact on the stability of ice surfaces and will most likely have an effect on ice surface reactivity as well as ice crystal growth and morphology. S Supplementary data are available from stacks.iop.org/JPhysCM/22/074209/mmedia

Artificial surfaces of intertwined square spirals:A CPW model

Intertwining planar spirals arranged in doubly periodic arrays enables a substantially subwavelength response of the unit cell smaller than 1/40 of wavelength with large fractional bandwidths. These properties are important for application at low frequencies, conformal curved surfaces, or with compact radiators. It is shown that interleaving counter-wound spiral arms extended into adjacent unit cells dramatically increase the array equivalent capacitance while reducing the inductance. A coplanar waveguide (CPW) model has been developed to analytically estimate the equivalent capacitance and inductance of intertwined spiral array elements in terms of their geometrical parameters. The proposed CPW model is shown to provide an accurate prediction of the fundamental resonance frequency and can be instrumental in the design of the arrays for a specified frequency response. © 2012 IEEE.

ARTIFICIAL SURFACES WITH INTERWOVEN AND TESSELLATED PATTERNED CONDUCTORS: PROPERTIES AND PHENOMENOLOGY

The features of artificial surfaces composed of doubly periodic patterns of interwoven planar conductors are discussed. The free-standing intertwined quadrifilar spirals and modified Brigid's crosses are presented as illustrative examples to demonstrate the highly stable angular reflection and transmittance response with low cross-polarisation and a broad fractional bandwidth. The main mechanisms contributing to the substantially sub-wavelength response of these arrays are discussed showing that interweaving their conductor patterns provides concurrent control of both the equivalent capacitance and inductance of the unit cell. The effects of dielectric substrate and conductor thickness on the properties of intertwined spiral and modified Brigid's cross arrays are discussed to provide insight in the effect of the structure parameters on array performance.

Electrical characterisation of liquid crystals at millimetre wavelengths using frequency selective surfaces

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The accurate measurement of the permittivity, loss tangent and dielectric anisotropy DC bias dependence for two different liquid crystal (LC) materials in the frequency range 140-165 GHz is described. The electrical characteristics are obtained by curve fitting computed transmission coefficients to the experimental spectral response of a new class of electronically reconfigurable frequency selective surface. The periodic structure is designed to yield bandpass filter characteristics with and without an applied bias control voltage in order to measure the tunability of the LC material which is inserted in a 705 µm-thick cavity.

‘Darkened surfaces’: camouflage and the nocturnal observation of Britain, 1941–45

Positioned in relation to an emerging geographical interest into the effects of different atmospheric and observational conditions in shaping sensory engagements with the Earth's surfaces, this paper considers how a critical examination of the practices of camouflage can open up new dialogues into how the Earth's surfaces become known, are interacted with, and transformed in the conditions of darkness. With an empirical focus on the cultural and historical geographies of nocturnal camouflage practised during the Second World War, the paper examines the systematic attempts of civil camoufleurs to understand how natural and artificial landforms were visibly 'present' in the nocturnal landscape, despite darkness often being conceived as producing an environment of 'visual absence' through diminished sensory engagement. Furthermore, the paper highlights how the tensions between visual presence/absence that shape both the nocturnal experience and the 'knowing' of landscape can often be exploited for social, cultural, and political ends, in this case, to enable protection against aerial attack. © 2013 Pion and its Licensors.

Electrochemical versus gas-phase oxidation of ru single-crystal surfaces

The electrochemical uptake of oxygen on a Ru(0001) electrode was investigated by electron diffraction, Auger spectroscopy, and cyclic voltammetry. An ordered (2 × 2)-O overlayer forms at a potential close to the hydrogen region. At +0.42 and +1.12 V vs Ag/AgCl, a (3 × 1) phase and a (1 × 1)-O phase, respectively, emerge. When the Ru electrode potential is maintained at +1.12 V for 2 min, RuO2 grows epitaxially with its (100) plane parallel to the Ru(0001) surface. In contrast to the RuO domains, the non-oxidized regions of the Ru electrode surface are flat. If, however, the electrode potential is increased to +1.98 V for 2 min, the remaining non-oxidized Ru area also becomes rough. These findings are compared with O overlayers and oxides on the Ru(0001) and Ru(101¯1) surfaces created by exposure to gaseous O under UHV conditions. On the other hand, gas-phase oxidation of the Ru(101¯0) surface leads to the formation of RuO with a (100) orientation. It is concluded that the difference in surface energy between RuO(110) and RuO(100) is quite small. RuO again grows epitaxially on Ru(0001), but with the (110) face oriented parallel to the Ru(0001) surface. The electrochemical oxidation of the Ru(0001) electrode surface proceeds via a 3-dimensional growth mechanism with a mean cluster size of 1.6 nm, whereas under UHV conditions, a 2-dimensional oxide film (1-2 nm thick) is epitaxially formed with an average domain size of 20 µm. © 2000 American Chemical Society.

Influence of surface structures, subsurface carbon and hydrogen, and surface alloying on the activity and selectivity of acetylene hydrogenation on Pd surfaces: A density functional theory study

The selective hydrogenation of acetylene to ethylene on several Pd surfaces (Pd(111), Pd(100), Pd(211), and Pd(211)-defect) and Pd surfaces with subsurface species (carbon and hydrogen) as well as a number of Pd-based alloys (Pd-M/Pd(111) and Pd-M/Pd(211) (M = Cu, Ag and Au)) are investigated using density functional theory calculations to understand both the acetylene hydrogenation activity and the selectivity of ethylene formation. All the hydrogenation barriers are calculated, and the reaction rates on these surfaces are obtained using a two-step model. Pd(211) is found to have the highest activity for acetylene hydrogenation while Pd(100) gives rise to the lowest activity. In addition, more open surfaces result in over-hydrogenation to form ethane, while the close-packed surface (Pd(111)) is the most selective. However, we also find that the presence of subsurface carbon and hydrogen significantly changes the reactivity and selectivity of acetylene toward hydrogenation on Pd surfaces. On forming surface alloys of Pd with Cu, Ag and Au, the selectivity for ethylene is also found to be changed. A new energy decomposition method is used to quantitatively analyze the factors in determining the changes in selectivity. These surface modifiers are found to block low coordination unselective sites, leading to a decreased ethane production. (C) 2013 The Authors. Published by Elsevier Inc. All rights reserved.

The effects of stepped sites and ruthenium adatom decoration on methanol dehydrogenation over platinum-based catalyst surfaces

A density functional theory study of methanol dehydrogenation over stepped Pt(2 1 1) surfaces without and with Ru modification was carried out to understand fuel catalytic reactions on Pt-based catalysts. Two main pathways of the CH3OH dehydrogenation were examined: the O–H pathway which was initiated by O–H bond scission to form the methoxy (CH3O) intermediate followed by sequential cleavage of C–H bonds to CO, and the C–H pathway which was initiated by C–H bond scission to form the hydroxymethyl (CH2OH) followed by two C–H bond cleavages to COH and then CO. Possible crossover reactions between the O–H and C–H pathways were also computed. Compared to flat Pt(1 1 1), stepped Pt(2 1 1) increases the adsorption energies of intermediates, making no significant contribution to decreasing the reaction barriers of most elementary steps involved, except in the first hydrogen scission. However, on the Ru-modified surface, a significant reduction was found in reaction barriers for the first step of the C–H bond scission and a number of further dehydrogenation steps crossing over to the O–H pathway, with the most facile paths identified. Our data reveals the complexity of methanol catalytic reaction processes at the atomic level and contributes to a fundamental understanding of fuel reactions on Pt-based catalysts.

Electrowetting movement of an aqueous droplet between two three-dimensional electrode surfaces

In an effort to develop a novel electronic paper image display technology based on the electrowetting principle, a 3-D electrowetting cell is designed and fabricated, which consists of two 3-D bent electrodes, each having a horizontal surface made of gold and a vertical surface made of indium tin oxide (ITO) glass as a color display window, a layer of dielectric material on the 3-D electrodes, and a highly fluorinated hydrophobic layer on the surface of the dielectric layer. Results of this work show that an electrowetting-induced motion of an aqueous droplet in immiscible oils can be achieved reversibly across the boundary of the horizontal and vertical surfaces of the 3-D electrode surface. It is also shown that the droplet can maintain its wetting state on a vertical sidewall electrode free of a power supplier when the voltage is removed. This phenomenon may form the basis for color contrast modulation applications, where a power-free image display is required, such as electronic paper display technology in the future. (C) 2009 Society of Photo-Optical Instrumentation Engineers. [DOI: 10.1117/1.3100201]

Universal tight binding model for chemical reactions in solution and at surfaces. II. Water

A revised water model intended for use in condensed phase simulations in the framework of the self consistent polarizable ion tight binding theory is constructed. The model is applied to water monomer, dimer, hexamers, ice, and liquid, where it demonstrates good agreement with theoretical results obtained by more accurate methods, such as DFT and CCSD(T), and with experiment. In particular, the temperature dependence of the self diffusion coefficient in liquid water predicted by the model, closely reproduces experimental curves in the temperature interval between 230 K and 350 K. In addition, and in contrast to standard DFT, the model properly orders the relative densities of liquid water and ice. A notable, but inevitable, shortcoming of the model is underestimation of the static dielectric constant by a factor of two. We demonstrate that the description of inter and intramolecular forces embodied in the tight binding approximation in quantum mechanics leads to a number of valuable insights which can be missing from ab initio quantum chemistry and classical force fields. These include a discussion of the origin of the enhanced molecular electric dipole moment in the condensed phases, and a detailed explanation for the increase of coordination number in liquid water as a function of temperature and compared with ice-leading to insights into the anomalous expansion on freezing. The theory holds out the prospect of an understanding of the currently unexplained density maximum of water near the freezing point.