A case of four-coordinate silver(I) adopting a high energy planar geometry. Experiment and theory

The ligands PhL and MeL are obtained by condensing 2-formylpyridine with benzil dihydrazone and diacetyl dihydrazone, respectively, in 2: 1 molar proportion. With silver( I), PhL yields a double-stranded dinuclear cationic helicate 1 in which the metal is tetrahedral but MeL gives a cationic one-dimensional polymeric complex 2 where silver( I) is distorted square planar and the ligand backbone is nearly planar. In both complexes, metal: ligand ratio is 1: 1. Ab initio calculations on the ligands at the HF/6-31+G* level reveal that while PhL strongly prefers a helical conformation, MeL has a natural inclination to remain in a planar conformation. Density functional theory calculations on model silver( I) complexes show that formation of the linear polymer in the case of MeL is also an important factor in imposing the planar geometry of Ag(I) in 2.

Surface geometry of Cu{531}

We present a combined quantitative low-energy electron diffraction (LEED) and density-functional theory (DFT) study of the chiral Cu{531} surface. The surface shows large inward relaxations with respect to the bulk interlayer distance of the first two layers and a large expansion of the distance between the fourth and fifth layers. (The latter is the first layer having the same coordination as the Cu atoms in the bulk.) Additional calculations have been performed to study the likelihood of faceting by comparing surface energies of possible facet terminations. No overall significant reduction in energy with respect to planar {531} could be found for any of the tested combinations of facets, which is in agreement with the experimental findings.

The local adsorption geometry and electronic structure of alanine on Cu{110}

The adsorption of alanine on Cu {110} was studied by a combination of near edge X-ray absorption fine structure (NEXAFS) spectroscopy, X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT). Large chemical shifts in the C 1s, N 1s, and O 1s XP spectra were found between the alanine multilayer and the chemisorbed and pseudo-(3 x 2) alaninate layers. From C, N, and O K-shell NEXAFS spectra the tilt angles of the carboxylate group (approximate to 26 degrees in plane with respect to [1 (1) over bar0] and approximate to 45 degrees out of plane) and the C-N bond angle with respect to [1 (1) over bar0] could be determined for the pseudo-(3 x 2) overlayer. Using this information three adsorption geometries could be eliminated from five p(3 x 2) structures which lead to almost identical heats of adsorption in the DFT calculations between 1.40 and 1.47 eV/molecule. Due to the small energy difference between the remaining two structures it is not unlikely that these coexist on the surface at room temperature. (c) 2006 Elsevier B.V. All rights reserved.

The adsorption geometry of sulphur on Ir{100}: a quantitative LEED study

A quantitative low energy electron diffraction (LEED) analysis has been performed for the p(2 x 2)-S and c(2 x 2)-S surface structures formed by exposing the (1 x 1) phase of Ir{100} to H2S at 750 K. S is found to adsorb on the fourfold hollow sites in both structures leading to Pendry R-factor values of 0.17 for the p(2 x 2)-S and 0.16 for the c(2 x 2)-S structures. The distances between S and the nearest and next-nearest Ir atoms were found to be similar in both structures: 2.36 +/- 0.01 angstrom and 3.33 +/- 0.01 angstrom, respectively. The buckling in the second substrate layer is consistent with other structural studies for S adsorption on fcc{100} transition metal surfaces: 0.09 angstrom for p(2 x 2)-S and 0.02 angstrom for c(2 x 2)-S structures. The (1 x 5) reconstruction, which is the most stable phase for clean Ir{100}, is completely lifted and a c(2 x 2)-S overlayer is formed after exposure to H,S at 300 K followed by annealing to 520 K. CO temperature-programmed desorption (TPD) experiments indicate that the major factor in the poisoning of Ir by S is site blocking. (c) 2005 Elsevier B.V. All rights reserved.

Facile strategies for the synthesis and crystallization of linear trinuclear nickel(II)-Schiff base, complexes with carboxylate bridges: Tuning of coordination geometry and magnetic properties

Three new linear trinuclear nickel(II) complexes, [Ni-3(salpen)(2)(OAc)(2)(H2O)(2)]center dot 4H(2)O (1) (OAc = acetate, CH3COO-), [Ni-3(salpen)(2)(OBz)(2)] (2) (OBz=benzoate, PhCOO-) and [Ni-3(salpen)(2)(OCn)(2)(CH3CN)(2)] (4) (OCn = cinnamate, PhCH=CHCOO-), H(2)salpen = tetradentate ligand, N,N'-bis(salicylidene)-1,3-pentanediamine have been synthesized and characterized structurally and magnetically. The choice of solvent for growing single crystal was made by inspecting the morphology of the initially obtained solids with the help of SEM study. The magnetic properties of a closely related complex, [Ni-3(salpen)(2)(OPh)(2)(EtOH)] (3) (OPh = phenyl acetate, PhCH2COO-) whose structure and solution properties have been reported recently, has also been studied here. The structural analyses reveal that both phenoxo and carboxylate bridging are present in all the complexes and the three Ni(II) atoms remain in linear disposition. Although the Schiff base ligand and the syn-syn bridging bidentate mode of the carboxylate group remain the same in complexes 1-4, the change of alkyl/aryl group of the carboxylates brings about systematic variations between six- and five-coordination in the geometry of the terminal Ni(II) centres of the trinuclear units. The steric demand as well as hydrophobic nature of the alkyl/aryl group of the carboxylate is found to play a crucial role in the tuning of the geometry. Variable-temperature (2-300 K) magnetic susceptibility measurements show that complexes 1-4 are antiferromagnetically coupled (J = -3.2(1), -4.6(1). -3.2(1) and -2.8(1) cm(-1) in 1-4, respectively). Calculations of the zero-field splitting parameter indicate that the values of D for complexes 1-4 are in the high range (D = +9.1(2), +14.2(2), +9.8(2) and +8.6(1) cm(-1) for 1-4, respectively). The highest D value of +14.2(2) and +9.8(2) cm(-1) for complexes 2 and 3, respectively, are consistent with the pentacoordinated geometry of the two terminal nickel(II) ions in 2 and one terminal nickel(II) ion in 3. (C) 2009 Elsevier Ltd. All rights reserved.

COMPUTER assisted technologies to enhance CONCURRENce in building DESIGN

Modern organisms are adapted to a wide variety of habitats and lifestyles. The processes of evolution have led to complex, interdependent, well-designed mechanisms of todays world and this research challenge is to transpose these innovative solutions to resolve problems in the context of architectural design practice, e.g., to relate design by nature with design by human. In a design by human environment, design synthesis can be performed with the use of rapid prototyping techniques that will enable to transform almost instantaneously any 2D design representation into a physical three-dimensional model, through a rapid prototyping printer machine. Rapid prototyping processes add layers of material one on top of another until a complete model is built and an analogy can be established with design by nature where the natural lay down of earth layers shapes the earth surface, a natural process occurring repeatedly over long periods of time. Concurrence in design will particularly benefit from rapid prototyping techniques, as the prime purpose of physical prototyping is to promptly assist iterative design, enabling design participants to work with a three-dimensional hardcopy and use it for the validation of their design-ideas. Concurrent design is a systematic approach aiming to facilitate the simultaneous involvment and commitment of all participants in the building design process, enabling both an effective reduction of time and costs at the design phase and a quality improvement of the design product. This paper presents the results of an exploratory survey investigating both how computer-aided design systems help designers to fully define the shape of their design-ideas and the extent of the application of rapid prototyping technologies coupled with Internet facilities by design practice. The findings suggest that design practitioners recognize that these technologies can greatly enhance concurrence in design, though acknowledging a lack of knowledge in relation to the issue of rapid prototyping.

Application of computer-aided facilities management (CAFM) for intelligent buildings operation

Purpose – The purpose of this paper is to investigate the concepts of intelligent buildings (IBs), and the opportunities offered by the application of computer-aided facilities management (CAFM) systems. Design/methodology/approach – In this paper definitions of IBs are investigated, particularly definitions that are embracing open standards for effective operational change, using a questionnaire survey. The survey further investigated the extension of CAFM to IBs concepts and the opportunities that such integrated systems will provide to facilities management (FM) professionals. Findings – The results showed variation in the understanding of the concept of IBs and the application of CAFM. The survey showed that 46 per cent of respondents use a CAFM system with a majority agreeing on the potential of CAFM in delivery of effective facilities. Research limitations/implications – The questionnaire survey results are limited to the views of the respondents within the context of FM in the UK. Practical implications – Following on the many definitions of an IB does not necessarily lead to technologies of equipment that conform to an open standard. This open standard and documentation of systems produced by vendors is the key to integrating CAFM with other building management systems (BMS) and further harnessing the application of CAFM for IBs. Originality/value – The paper gives experience-based suggestions for both demand and supply sides of the service procurement to gain the feasible benefits and avoid the currently hindering obstacles, as the paper provides insight to the current and future tools for the mobile aspects of FM. The findings are relevant for service providers and operators as well.

The geometry of optimal control solutions on some six dimensional lie groups

This paper examines optimal solutions of control systems with drift defined on the orthonormal frame bundle of particular Riemannian manifolds of constant curvature. The manifolds considered here are the space forms Euclidean space E-3, the spheres S-3 and the hyperboloids H-3 with the corresponding frame bundles equal to the Euclidean group of motions SE(3), the rotation group SO(4) and the Lorentz group SO(1,3). The optimal controls of these systems are solved explicitly in terms of elliptic functions. In this paper, a geometric interpretation of the extremal solutions is given with particular emphasis to a singularity in the explicit solutions. Using a reduced form of the Casimir functions the geometry of these solutions are illustrated.

Therapeutic potential of computer to cerebral cortex implantable devices

In this article, an overview of some of the latest developments in the field of cerebral cortex to computer interfacing (CCCI) is given. This is posed in the more general context of Brain-Computer Interfaces in order to assess advantages and disadvantages. The emphasis is clearly placed on practical studies that have been undertaken and reported on, as opposed to those speculated, simulated or proposed as future projects. Related areas are discussed briefly only in the context of their contribution to the studies being undertaken. The area of focus is notably the use of invasive implant technology, where a connection is made directly with the cerebral cortex and/or nervous system. Tests and experimentation which do not involve human subjects are invariably carried out a priori to indicate the eventual possibilities before human subjects are themselves involved. Some of the more pertinent animal studies from this area are discussed. The paper goes on to describe human experimentation, in which neural implants have linked the human nervous system bidirectionally with technology and the internet. A view is taken as to the prospects for the future for CCCI, in terms of its broad therapeutic role.

Perspex machine VII: The universal perspex machine

The perspex machine arose from the unification of projective geometry with the Turing machine. It uses a total arithmetic, called transreal arithmetic, that contains real arithmetic and allows division by zero. Transreal arithmetic is redefined here. The new arithmetic has both a positive and a negative infinity which lie at the extremes of the number line, and a number nullity that lies off the number line. We prove that nullity, 0/0, is a number. Hence a number may have one of four signs: negative, zero, positive, or nullity. It is, therefore, impossible to encode the sign of a number in one bit, as floating-, point arithmetic attempts to do, resulting in the difficulty of having both positive and negative zeros and NaNs. Transrational arithmetic is consistent with Cantor arithmetic. In an extension to real arithmetic, the product of zero, an infinity, or nullity with its reciprocal is nullity, not unity. This avoids the usual contradictions that follow from allowing division by zero. Transreal arithmetic has a fixed algebraic structure and does not admit options as IEEE, floating-point arithmetic does. Most significantly, nullity has a simple semantics that is related to zero. Zero means "no value" and nullity means "no information." We argue that nullity is as useful to a manufactured computer as zero is to a human computer. The perspex machine is intended to offer one solution to the mind-body problem by showing how the computable aspects of mind and. perhaps, the whole of mind relates to the geometrical aspects of body and, perhaps, the whole of body. We review some of Turing's writings and show that he held the view that his machine has spatial properties. In particular, that it has the property of being a 7D lattice of compact spaces. Thus, we read Turing as believing that his machine relates computation to geometrical bodies. We simplify the perspex machine by substituting an augmented Euclidean geometry for projective geometry. This leads to a general-linear perspex-machine which is very much easier to pro-ram than the original perspex-machine. We then show how to map the whole of perspex space into a unit cube. This allows us to construct a fractal of perspex machines with the cardinality of a real-numbered line or space. This fractal is the universal perspex machine. It can solve, in unit time, the halting problem for itself and for all perspex machines instantiated in real-numbered space, including all Turing machines. We cite an experiment that has been proposed to test the physical reality of the perspex machine's model of time, but we make no claim that the physical universe works this way or that it has the cardinality of the perspex machine. We leave it that the perspex machine provides an upper bound on the computational properties of physical things, including manufactured computers and biological organisms, that have a cardinality no greater than the real-number line.