Lanthanide complexes of 2-hydroxynicotinic acid: synthesis, luminescence properties and the crystal structures of [Ln(HnicO)(2)(mu-HnicO)(H2O)] center dot nH(2)O (Ln = Tb, Eu)

New lanthanide complexes of 2-hydroxynicotinic acid (H(2)nicO) [Ln(HnicO)(2)(mu-HnicO)(H2O)] (.) nH(2)O (Ln = Eu, Gd, Tb, Er, Tm) were prepared. The crystal structures of the [Tb(HnicO)(2)(g-HnicO)(H2O)] (.) 1.75H(2)O(1) and [Eu(HniCO)(2)(mu-HnicO)(H2O)] (.) 1.25H(2)O (2) complexes were determined by X-ray diffraction. The 2-hydroxynicotinate ligand coordinates through O,O-chelation to the lanthanide(III) ions as shown by X-ray diffraction and the infrared, Raman and NMR spectroscopy results. Photoluminescence measurements were performed for the Eu(III) and Tb(III) complexes. Lifetimes of 0.592 +/- 0.007 and 0.113 +/- 0.002 ms were determined for the Eu3+ and Tb3+ emitting states D-5(0) and D-5(4), respectively. A value around 30% was found for the D-5(0) quantum efficiency. The energy transfer mechanisms between the lanthanide ions and the ligands are discussed and compared with those observed in similar complexes involving the 3-hydroxypicolinate ligand based on the luminescence of the respective Gd3+-based complexes. (C) 2003 Published by Elsevier Ltd.

A reaction surface Hamiltonian study of malonaldehyde

We report calculations using a reaction surface Hamiltonian for which the vibrations of a molecule are represented by 3N-8 normal coordinates, Q, and two large amplitude motions, s(1) and s(2). The exact form of the kinetic energy operator is derived in these coordinates. The potential surface is first represented as a quadratic in Q, the coefficients of which depend upon the values of s(1),s(2) and then extended to include up to Q(6) diagonal anharmonic terms. The vibrational energy levels are evaluated by solving the variational secular equations, using a basis of products of Hermite polynomials and appropriate functions of s(1),s(2). Our selected example is malonaldehyde (N=9) and we choose as surface parameters two OH distances of the migrating H in the internal hydrogen transfer. The reaction surface Hamiltonian is ideally suited to the study of the kind of tunneling dynamics present in malonaldehyde. Our results are in good agreement with previous calculations of the zero point tunneling splitting and in general agreement with observed data. Interpretation of our two-dimensional reaction surface states suggests that the OH stretching fundamental is incorrectly assigned in the infrared spectrum. This mode appears at a much lower frequency in our calculations due to substantial transition state character. (c) 2006 American Institute of Physics.

The vibrations and tunnelling of malonaldehyde on a Moller-Plesset surface

The vibrations and tunnelling motion of malonaldehyde have been studied in their full dimensionality using an internal coordinate path Hamiltonian. In this representation there is one large amplitude internal coordinate s and 3N - 7 (=20) normal coordinates Q which are orthogonal to the large amplitude motion at all points. It is crucial that a high accuracy potential energy surface is used in order to obtain a good representation for the tunneling motion; we use a Moller-Plesset (MP2) surface. Our methodology is variational, that is we diagonalize a sufficiently large matrix in order to obtain the required vibrational levels, so an exact representation for the kinetic energy operator is used. In a harmonic valley representation (s, Q) complete convergence of the normal coordinate motions and the internal coordinate motions has been obtained; for the anharmonic valley in which we use two- and three-body terms in the surface (s, Q(1), Q(2)), we also obtain complete convergence. Our final computed stretching fundamentals are deficient because our potential energy surface is truncated at quartic terms in the normal coordinates, but our lower fundamentals are good.

Tests of MULTIMODE calculations of rovibrational energies of CH4

We report variational calculations of rovibrational energies of CH4 using the code MULTIMODE and an ab initio force field of Schwenke and Partridge. The systematic convergence of the energies with respect to the level of mode coupling is presented. Converged vibrational energies calculated using the five-mode representation of the potential for zero total angular momentum are compared with previous, benchmark calculations based on Radau coordinates using this force field for zero total angular momentum and for J = 1. Very good agreement with the previous benchmark calculations is found. (c) 2006 Elsevier B.V. All rights reserved.

Marker placement to describe the wrist movements during activities of daily living in cyclical tasks

Objective. To describe the wrist kinematics during movement through free range of motion and activities of daily living using a cyclical task. Design. The wrist angles were initially calculated in a calibration trial and then in two selected activities of daily living (jar opening and carton pouring). Background. Existing studies which describe the wrist movement do not address the specific application of daily activities. Moreover, the data presented from subject to subject may differ simply because of the non-cyclical nature of the upper limbs movements. Methods. The coordinates of external markers attached to bone references on the forearm and dorsal side of the hand were obtained using an optical motion capture system. The wrist angles were derived from free motion trials and successively calculated in four healthy subjects for two specific cyclical daily activities (opening a jar and pouring from a carton). Results. The free motions trial highlighted the interaction between the wrist angles. Both the jar opening and the carton pouring activity showed a repetitive pattern for the three angles within the cycle length. In the jar-opening task, the standard deviation for the whole population was 10.8degrees for flexion-extension, 5.3degrees for radial-ulnar deviation and 10.4degrees for pronation-supination. In the carton-pouring task, the standard deviation for the whole population was 16.0degrees for flexion-extension, 3.4degrees for radial-ulnar deviation and 10.7degrees for pro nation-supination. Conclusion. Wrist kinematics in healthy subjects can be successfully described by the rotations about the axes of marker-defined coordinates systems during free range of motion and daily activities using cyclical tasks.

The exclusive use of integer-order spots for LEED-IV structure analysis of adsorption systems: p(2×2)-O on Ni{111}

Two different ways of performing low-energy electron diffraction (LEED) structure determinations for the p(2 x 2) structure of oxygen on Ni {111} are compared: a conventional LEED-IV structure analysis using integer and fractional-order IV-curves collected at normal incidence and an analysis using only integer-order IV-curves collected at three different angles of incidence. A clear discrimination between different adsorption sites can be achieved by the latter approach as well as the first and the best fit structures of both analyses are within each other's error bars (all less than 0.1 angstrom). The conventional analysis is more sensitive to the adsorbate coordinates and lateral parameters of the substrate atoms whereas the integer-order-based analysis is more sensitive to the vertical coordinates of substrate atoms. Adsorbate-related contributions to the intensities of integer-order diffraction spots are independent of the state of long-range order in the adsorbate layer. These results show, therefore, that for lattice-gas disordered adsorbate layers, for which only integer-order spots are observed, similar accuracy and reliability can be achieved as for ordered adsorbate layers, provided the data set is large enough.

Stability of solutions of linear difference equations with periodic coefficients

This paper represents the last technical contribution of Professor Patrick Parks before his untimely death in February 1995. The remaining authors of the paper, which was subsequently completed, wish to dedicate the article to Patrick. A frequency criterion for the stability of solutions of linear difference equations with periodic coefficients is established. The stability criterion is based on a consideration of the behaviour of a frequency hodograph with respect to the origin of coordinates in the complex plane. The formulation of this criterion does not depend on the order of the difference equation.

Representing geometrical knowledge

This paper introduces perspex algebra which is being developed as a common representation of geometrical knowledge. A perspex can currently be interpreted in one of four ways. First, the algebraic perspex is a generalization of matrices, it provides the most general representation for all of the interpretations of a perspex. The algebraic perspex can be used to describe arbitrary sets of coordinates. The remaining three interpretations of the perspex are all related to square matrices and operate in a Euclidean model of projective space-time, called perspex space. Perspex space differs from the usual Euclidean model of projective space in that it contains the point at nullity. It is argued that the point at nullity is necessary for a consistent account of perspective in top-down vision. Second, the geometric perspex is a simplex in perspex space. It can be used as a primitive building block for shapes, or as a way of recording landmarks on shapes. Third, the transformational perspex describes linear transformations in perspex space that provide the affine and perspective transformations in space-time. It can be used to match a prototype shape to an image, even in so called 'accidental' views where the depth of an object disappears from view, or an object stays in the same place across time. Fourth, the parametric perspex describes the geometric and transformational perspexes in terms of parameters that are related to everyday English descriptions. The parametric perspex can be used to obtain both continuous and categorical perception of objects. The paper ends with a discussion of issues related to using a perspex to describe logic.

Complete robot-eye calibration without special calibration objects

A robot mounted camera is useful in many machine vision tasks as it allows control over view direction and position. In this paper we report a technique for calibrating both the robot and the camera using only a single corresponding point. All existing head-eye calibration systems we have encountered rely on using pre-calibrated robots, pre- calibrated cameras, special calibration objects or combinations of these. Our method avoids using large scale non-linear optimizations by recovering the parameters in small dependent groups. This is done by performing a series of planned, but initially uncalibrated robot movements. Many of the kinematic parameters are obtained using only camera views in which the calibration feature is at, or near the image center, thus avoiding errors which could be introduced by lens distortion. The calibration is shown to be both stable and accurate. The robotic system we use consists of camera with pan-tilt capability mounted on a Cartesian robot, providing a total of 5 degrees of freedom.

Self-consistent field theory for diblock copolymers grafted to a sphere

An efficient numerical self-consistent field theory (SCFT) algorithm is developed for treating structured polymers on spherical surfaces. The method solves the diffusion equations of SCFT with a pseudospectral approach that combines a spherical-harmonics expansion for the angular coordinates with a modified real-space Crank–Nicolson method for the radial direction. The self-consistent field equations are solved with Anderson-mixing iterations using dynamical parameters and an alignment procedure to prevent angular drift of the solution. A demonstration of the algorithm is provided for thin films of diblock copolymer grafted to the surface of a spherical core, in which the sequence of equilibrium morphologies is predicted as a function of diblock composition. The study reveals an array of interesting behaviors as the block copolymer pattern is forced to adapt to the finite surface area of the sphere.

View-based modelling of human visual navigation errors

View-based and Cartesian representations provide rival accounts of visual navigation in humans, and here we explore possible models for the view-based case. A visual “homing” experiment was undertaken by human participants in immersive virtual reality. The distributions of end-point errors on the ground plane differed significantly in shape and extent depending on visual landmark configuration and relative goal location. A model based on simple visual cues captures important characteristics of these distributions. Augmenting visual features to include 3D elements such as stereo and motion parallax result in a set of models that describe the data accurately, demonstrating the effectiveness of a view-based approach.

Children, futurity, and value: 'Adventures of Huckleberry Finn'

A recurrent but relatively unquestioned element in the canonisation of Adventures of Huckleberry Finn is that the novel is about securing a meaningful way forward for the American child. The sense is that the novel deserves to live and to have a future because it is about a child, and tied in with the need for the young nation to project and to determine its future. This might seem, to apply the terms of queer debate, to lend weight to ‘reproductive futurism’: the child and ‘American family values’ are to the fore, while sexual minorities and alternative social models are excluded. The present essay re-reads Huckleberry Finn and Twain’s other Huck narratives, using the coordinates of queer theory. The result is a more equivocal picture. Twain does use Huck to assert the rights of the white American family, but he also uses him to explore alternative ideas of social organisation. More fundamentally, Twain increasingly finds that the idea of the child is no longer a sufficient motive for believing in and projecting a future. Rather, his writing leads the reader towards the impossibility of the future, both for the nation and its child.

Three dimensional picture of the local structure of 1,4-Polybutadiene from a complete atomistic model and neutron scattering data

An efficient method of combining neutron diffraction data over an extended Q range with detailed atomistic models is presented. A quantitative and qualitative mapping of the organization of the chain conformation in both glass and liquid phase has been performed. The proposed structural refinement method is based on the exploitation of the intrachain features of the diffraction pattern by the use of internal coordinates for bond lengths, valence angles and torsion rotations. Models are built stochastically by assignment of these internal coordinates from probability distributions with limited variable parameters. Variation of these parameters is used in the construction of models that minimize the differences between the observed and calculated structure factors. A series of neutron scattering data of 1,4-polybutadiene at the region 20320 K is presented. Analysis of the experimental data yield bond lengths for C-C and C=C of 1.54 and 1.35 Å respectively. Valence angles of the backbone were found to be at 112 and 122.8 for the CCC and CC=C respectively. Three torsion angles corresponding to the double bond and the adjacent R and β bonds were found to occupy cis and trans, s(, trans and g( and trans states, respectively. We compare our results with theoretical predictions, computer simulations, RIS models, and previously reported experimental results.

Eigenstructure assignment in descriptor systems

Coordinate free conditions are given for pole assignment by feedback in linear descriptor (singular) systems which guarantee closed-loop regularity. These conditions are shown to be both necessary and sufficient for assignment of the maximum possible number of finite poles. Transformation to special coordinates are not used and the results provide a robust algorithm for the computation of the required feedback.

Structure and magnetic properties of an unprecedented syn-antiμ-nitrito-1κO:2κO′ bridged Mn(iii)-salen complex and its isoelectronic and isostructural formate analogue

The preparation, crystal structures and magnetic properties of two new isoelectronic and isomorphous formate-and nitrite-bridged 1D chains of Mn(III)-salen complexes, [Mn(salen)(HCOO)](n) (1) and [Mn(salen)(NO2)](n) (2), where salen is the dianion of N,N'-bis(salicylidene)-1,2-diaminoethane, are presented. The structures show that the salen ligand coordinates to the four equatorial sites of the metal ion and the formate or nitrite ions coordinate to the axial positions to bridge the Mn(III)-salen units through a syn-anti mu-1 kappa O:2 kappa O' coordination mode. Such a bridging mode is unprecedented in Mn(III) for formate and in any transition metal ion for nitrite. Variable-temperature magnetic susceptibility measurements of complexes 1 and 2 indicate the presence of ferromagnetic exchange interactions with J values of 0.0607 cm(-1) (for 1) and 0.0883 cm(-1) (for 2). The ac measurements indicate negligible frequency dependence for 1 whereas compound 2 exhibits a decrease of chi(ac)' and a concomitant increase of chi(ac)'' on elevating frequency around 2 K. This finding is an indication of slow magnetization reversal characteristic of single-chain magnets or spin-glasses. The mu-nitrito-1 kappa O:2 kappa O' bridge seems to be a potentially superior magnetic coupler to the formate bridge for the construction of single-molecule/-chain magnets as its coupling constant is greater and the chi(ac)' and chi(ac)'' show frequency dependence.