Older male and female drivers in car-dependent settings: How much do they use other modes, and do they compensate for reduced driving to maintain mobility?

Among the societal and health challenges of population ageing is the continued transport mobility of older people who retain their driving licence, especially in highly car-dependent societies. While issues surrounding loss of a driving licence have been researched, less attention has been paid to variations in physical travel by mode among the growing proportion of older people who retain their driving licence. It is unclear how much they reduce their driving with age, the degree to which they replace driving with other modes of transport, and how this varies by age and gender. This paper reports research conducted in the state of Queensland, Australia, with a sample of 295 older drivers (>60 years). Time spent driving is considerably greater than time spent as a passenger or walking across age groups and genders. A decline in travel time as a driver with increasing age is not redressed by increases in travel as a passenger or pedestrian. The patterns differ by gender, most likely reflecting demographic and social factors. Given the expected considerable increase in the number of older women in particular, and their reported preference not to drive alone, there are implications for policies and programmes that are relevant to other car-dependent settings. There are also implications for the health of older drivers, since levels of walking are comparatively low.

The partition of unity finite element method for elastic wave propagation in Reissner-Mindlin plates

This paper reports a numerical method for modelling the elastic wave propagation in plates. The method is based on the partition of unity approach, in which the approximate spectral properties of the infinite dimensional system are embedded within the space of a conventional finite element method through a consistent technique of waveform enrichment. The technique is general, such that it can be applied to the Lagrangian family of finite elements with specific waveform enrichment schemes, depending on the dominant modes of wave propagation in the physical system. A four-noded element for the Reissner-indlin plate is derived in this paper, which is free of shear locking. Such a locking-free property is achieved by removing the transverse displacement degrees of freedom from the element nodal variables and by recovering the same through a line integral and a weak constraint in the frequency domain. As a result, the frequency-dependent stiffness matrix and the mass matrix are obtained, which capture the higher frequency response with even coarse meshes, accurately. The steps involved in the numerical implementation of such element are discussed in details. Numerical studies on the performance of the proposed element are reported by considering a number of cases, which show very good accuracy and low computational cost. Copyright (C)006 John Wiley & Sons, Ltd.

Manifestation of conical intersections in resonance Raman intensities

This paper deals with the manifestations of conical intersections (CIs), unequivocal spectroscopic signatures of which are still elusive, in the resonance Raman intensities. In particular, the results of our calculations on the `two state-two vibrational mode' and the `two state-three vibrational mode' models are presented. The models comprise two excited states of different spatial symmetry, one bright and one dark, which are coupled by a nontotally symmetric mode while the energy gap between them is tuned by one/two totally symmetric modes. Time dependent theory for vibronically coupled states is employed for the calculation and analysis of Raman excitation profiles (REPs). The manifestation of intersections in REPs is studied by extensive modelm calculations and the results of two specific models are presented. Themfeasibility of using REPs to probe the role of CIs in polyatomic systems is ascertained by multimode calculations on two polyatomic systems viz., pyrazine and trans-azobenzene. The study also notes the importance of the pump excitation wavelength dependence in a femtosecond time-resolved experiment probing the intersection-induced nonadiabatic dynamics. Copyright (C) 2009 John Wiley & Sons, Ltd.

Measurements of branching fraction ratios and CP asymmetries in B±→DCPK± decays in hadron collisions

We reconstruct B+/- -> D K+/- decays in a data sample collected by the CDF II detector at the Tevatron collider corresponding to 1 fb-1 of integrated luminosity. We select decay modes where the D meson decays to either K- pi+ (flavor eigenstate) or K- K+, pi- pi+ (CP-even eigenstates), and measure the direct CP asymmetry A_CP+ = 0.39 +/- 0.17(stat) +/- 0.04(syst), and the double ratio of CP-even to flavor eigenstate branching fractions R_CP+ = 1.30 +/- 0.24(stat) +/- 0.12(syst). These measurements will improve the determination of the CKM angle gamma. They are performed here for the first time using data from hadron collisions.

Two-Phase Thermodynamic Model for Efficient and Accurate Absolute Entropy of Water from Molecular Dynamics Simulations

Presented here is the two-phase thermodynamic (2PT) model for the calculation of energy and entropy of molecular fluids from the trajectory of molecular dynamics (MD) simulations. In this method, the density of state (DoS) functions (including the normal modes of translation, rotation, and intramolecular vibration motions) are determined from the Fourier transform of the corresponding velocity autocorrelation functions. A fluidicity parameter (f), extracted from the thermodynamic state of the system derived from the same MD, is used to partition the translation and rotation modes into a diffusive, gas-like component (with 3Nf degrees of freedom) and a nondiffusive, solid-like component. The thermodynamic properties, including the absolute value of entropy, are then obtained by applying quantum statistics to the solid component and applying hard sphere/rigid rotor thermodynamics to the gas component. The 2PT method produces exact thermodynamic properties of the system in two limiting states: the nondiffusive solid state (where the fluidicity is zero) and the ideal gas state (where the fluidicity becomes unity). We examine the 2PT entropy for various water models (F3C, SPC, SPC/E, TIP3P, and TIP4P-Ew) at ambient conditions and find good agreement with literature results obtained based on other simulation techniques. We also validate the entropy of water in the liquid and vapor phases along the vapor-liquid equilibrium curve from the triple point to the critical point. We show that this method produces converged liquid phase entropy in tens of picoseconds, making it an efficient means for extracting thermodynamic properties from MD simulations.

Molecular theory of solvation and solvation dynamics of a classical ion in a dipolar liquid

A microscopic theory of equilibrium solvation and solvation dynamics of a classical, polar, solute molecule in dipolar solvent is presented. Density functional theory is used to explicitly calculate the polarization structure around a solvated ion. The calculated solvent polarization structure is different from the continuum model prediction in several respects. The value of the polarization at the surface of the ion is less than the continuum value. The solvent polarization also exhibits small oscillations in space near the ion. We show that, under certain approximations, our linear equilibrium theory reduces to the nonlocal electrostatic theory, with the dielectric function (c(k)) of the liquid now wave vector (k) dependent. It is further shown that the nonlocal electrostatic estimate of solvation energy, with a microscopic c(k), is close to the estimate of linearized equilibrium theories of polar liquids. The study of solvation dynamics is based on a generalized Smoluchowski equation with a mean-field force term to take into account the effects of intermolecular interactions. This study incorporates the local distortion of the solvent structure near the ion and also the effects of the translational modes of the solvent molecules.The latter contribution, if significant, can considerably accelerate the relaxation of solvent polarization and can even give rise to a long time decay that agrees with the continuum model prediction. The significance of these results is discussed.

X-Ray structure of a ternary complex, copper(II)–lnosine 5-monophosphate–benzimidazole. The first example for the absence of direct metal–nucleotide interaction

The unprecedented absence of direct metal–nucleotide interaction has been observed in the X-ray structure of the ternary metal nucleotide system [Cu(bzim)(H2O)5]2+[IMP]2–·3H2O [IMP = inosine 5-monophosphate(2–), bzim = benzimidazole). The complex crystallizes in the space group P21 with a= 7.013(2), b= 13.179(9), c= 14.565(9)Å, = 94.82(4)°, and Z= 2. The structure was solved by the heavy-atom method and refined by full-matrix least squares on the basis of 1 761 observed (I? 3i) reflections to final R and R values of 0.034 and 0.036 respectively. The CuII has a distorted octahedral co-ordination with a nitrogen of the bzim ligand [Cu–N 1.947(5)Å] and three oxygens of water molecules in the basal plane [mean Cu–O 2.017(3)Å] and two more water oxygens at axial positions [Cu–O 2.194(6) and 2.732(5)Å]. The nucleotide base stacks with the bzim ligand at an average distance of 3.5 Å and an angle of 22°. In the lattice, N(7) of the base is linked to a lattice water through a hydrogen bond, while all the phosphate oxygens are involved in hydrogen bonds with co-ordinated as well as lattice water molecules. The co-ordination behaviour of IMP to CuII is compared in structures containing different -aromatic amines in order to assess the influence of the ternary ligand in complex formation. The present results indicate that, apart from the commonly observed phosphate binding, other modes of co-ordination are possible, these being influenced mainly by the -accepting properties of the ternary ligand.

Voltage delay during constant-current or constant-resistance discharge of Mg-MnO2 dry cells: A comparative study

A theoretical approach has been developed to relate the voltage delay transients of the Mg-MnO2 dry cell observed during discharge by two commonly employed modes, viz., (1) at constant current, and (2) across a constant resistance. The approach has been verified by comparison of experimentally obtained transients with those generated from theory. The method may be used to predict the delay parameters of the Mg-MnO2 dry cell under the two modes of discharge and can, in principle, be extended to lithium batteries.

Static and dynamic properties of incommensurate smectic-AIC liquid crystals

We study the elasticity, topological defects, and hydrodynamics of the recently discovered incommensurate smectic (AIC) phase, characterized by two collinear mass density waves of incommensurate spatial frequency. The low-energy long-wavelength excitations of the system can be described by a displacement field u(x) and a ��phason�� field w(x) associated, respectively, with collective and relative motion of the two constituent density waves. We formulate the elastic free energy in terms of these two variables and find that when w=0, its functional dependence on u is identical to that of a conventional smectic liquid crystal, while when u=0, its functional dependence on w is the same as that for the angle variable in a slightly anisotropic XY model. An arbitrariness in the definition of u and w allows a choice that eliminates all relevant couplings between them in the long-wavelength elastic energy. The topological defects of the system are dislocations with nonzero u and w components. We introduce a two-dimensional Burgers lattice for these dislocations, and compute the interaction between them. This has two parts: one arising from the u field that is short ranged and identical to the interaction between dislocations in an ordinary smectic liquid crystal, and one arising from the w field that is long ranged and identical to the logarithmic interaction between vortices in an XY model. The hydrodynamic modes of the AIC include first- and second-sound modes whose direction-dependent velocities are identical to those in ordinary smectics. The sound attenuations have a different direction dependence, however. The breakdown of hydrodynamics found in conventional smectic liquid crystals, with three of the five viscosities diverging as 1/? at small frequencies ?, occurs in these systems as well and is identical in all its details. In addition, there is a diffusive phason mode, not found in ordinary smectic liquid crystals, that leads to anomalously slow mechanical response analogous to that predicted in quasicrystals, but on a far more experimentally accessible time scale.

Governmental rationalities and the local dimension of European politics. A study of the Interreg IV programme "Alpenrhein-Bodensee-Hochrhein"

The thesis aims at investigating the local dimension of the EU cohesion policy through the utilization of an alternative approach, which aims at the analysis of discourse and structures of power. The concrete case under analysis is the Interreg IV programme “Alpenrhein-Bodensee-Hochrhein”, which is conducted in the border region between Germany, Switzerland, Austria and the principality of Liechtenstein. The main research question is stated as such: What governmental rationalities can be found at work in the field of EU cross-border cooperation programmes? How is directive action and cooperation envisioned? How coherent are the different rationalities, which are found at work? The theoretical framework is based on a Foucaultian understanding of power and discourse and utilizes the notion of governmentalities as a way to de-stabilize the understanding of directive action and in order to highlight the dispersed and heterogeneous nature of governmental activity. The approach is situated within the general field of research on the European Union connected to basic conceptualisations such as the nature of power, the role of discourse and modes of subjectification. An approach termed “analytics of government”, based on the work of researchers like Mitchell Dean is introduced as the basic framework for the analysis. Four dimensions (visiblities, subjectivities, techniques/practices, problematisations) are presented as a set of tools with which governmental regimes of practices can be analysed. The empirical part of the thesis starts out with a discussion of the general framework of the European Union's cohesion policy and places the Interreg IV Alpenrhein-Bodensee-Hochrhein programme in this general context. The main analysis is based on eleven interviews which were conducted with different individuals, participating in the programme on different levels. The selection of interview partners aimed at maximising heterogeneity through including individuals from all parts of the programme region, obtaining different functions within the programme. The analysis reveals interesting aspects pertaining to the implementation and routine aspects of work within initiatives conducted under the heading of the EU cohesion policy. The central aspects of an Interreg IV Alpenrhein-Bodensee-Hochrhein – governmentality are sketched out. This includes a positive perception of the work atmosphere, administrative/professional characterisation of the selves and a de-politicization of the programme. Characteristic is the experience of tensions by interview partners and the use of discoursive strategies to resolve them. Negative perceptions play an important role for the specific governmental rationality. The thesis contributes to a better understanding of the local dimension of the European Union cohesion policy and questions established ways of thinking about governmental activity. It provides an insight into the working of power mechanisms in the constitution of fields of discourse and points out matters of practical importance as well as subsequent research questions.

Use of 2-pyrimidineamidoxime to generate polynuclear homo-/heterometallic assemblies: synthesis, crystal structures and magnetic study with theoretical investigations on the exchange mechanism

Three new transition metal complexes using 2-pyrimidineamidoxime (pmadH(2)) as multidentate chelating and/or bridging ligand have been synthesized and characterized. The ligand pmadH(2) has two potential bridging functional groups mu-O and mu-(N-O)] and consequently shows several coordination modes. While a polymeric 1D Cu-II complex Cu(pmadH(2))(2)(NO3)](NO3) (1) was obtained upon treatment of Cu(NO3)(2)center dot 3H(2)O with pmadH(2) at room temperature in the absence of base, a high temperature reaction in the presence of base yielded a tetranuclear Cu-II-complex Cu-4(pmad)(2)(pmadH)(2)(NO3)](NO3)(H2O) (2). One of the Cu-II centers is in a square pyramidal environment while the other three are in a square planar geometry. Reaction of the same ligand with an equimolar mixture of both Cu(NO3)(2)center dot 3H(2)O and NiCl2 center dot 6H(2)O yielded a tetranuclear heterometallic (Cu2Ni2II)-Ni-II complex Cu2Ni2(pmad)(2)(pmadH)(2)Cl-2]center dot H2O (3) containing both square planar (Ni-II) and square pyramidal (Cu-II) metal centers. Complexes 1-3 represent the first examples of polynuclear metal complexes of 2-pyrimidineamidoxime. The analysis of variable temperature magnetic susceptibility data of 2 reveals that both ferromagnetic and antiferromagnetic interactions exist in this complex (J(1) = +10.7 cm(-1) and J(2) = -2.7 cm(-1) with g = 2.1) leading to a resultant ferromagnetic behavior. Complex 3 shows expected antiferromagnetic interaction between two Cu-II centers through -N-O- bridging pathway with J(1) = -3.4 cm(-1) and g = 2.08. DFT calculations have been used to corroborate the magnetic results.

Vibrational Spectra and Assignments for the Fundamental Vibrations of Imidazolidine-2-thione and -2-selenone

Infrared spectra of imidazolidine-2-thione (N,N?-ethylenethiourea, ETU) and its N,N?-deuterated (ETU-d2) and S-methylthiouronium iodides have been recorded from 4000 to 30 cm?1. Normal coordinate analyses of ETU and ETU-d2 have been made for all the fundamental frequencies, employing a Urey-Bradley potential function supplemented with valence type constants for the out of plane modes of the planar skeleton. Raman frequencies of ETU from literature have been utilised. The results of the vibrational analyses are discussed in relation to the group frequencies in structurally related molecules and frequency shifts on deuteration and S-methylation. The normal coordinate treatment is also performed for the planar vibrations of imidazolidine-2-selenone (N,N?-ethyleneselenourea, ESU) to propose assignments for ESU and so also to support the assignments of ETU.

Characterization of a large-area PVDF thin film for electro-mechanical and ultrasonic sensing applications

Large-area PVDF thin films have been prepared and characterized for quasi-static and high frequency dynamic strain sensing applications. These films are prepared using hot press method and the piezoelectric phase (beta-phase) has been achieved by thermo-mechanical treatment and poling under DC field. The fabricated films have been characterized for quasi-static strain sensing and the linear strain-voltage relationship obtained is promising. In order to evaluate the ultrasonic sensing properties, a PZT wafer has been used to launch Lamb waves in a metal beam on which the PVDF film sensor is bonded at a distance. The voltage signals obtained from the PVDF films have been compared with another PZT wafer sensor placed on the opposite surface of the beam as a reference signal. Due to higher stiffness and higher thickness of the PZT wafer sensors, certain resonance patterns significantly degrade the sensor sensitivity curves. Whereas, the present results show that the large-area PVDF sensors can be superior with the signal amplitude comparable to that of PZT sensors and with no resonance-induced effect, which is due to low mechanical impedance, smaller thickness and larger area of the PVDF film. Moreover, the developed PVDF sensors are able to capture both A(0) and S-0 modes of Lamb wave, whereas the PZT sensors captures only A(0) mode in the same scale of voltage output. This shows promises in using large-area PVDF films with various surface patterns on structures for distributed sensing and structural health monitoring under quasi-static, vibration and ultrasonic situations. (C) 2010 Elsevier B.V. All rights reserved.

Syntheses, X-ray structure and properties of (5-cyclopentadienyl)ruthenium(II) complexes of pyridyl-2-hydrazone ligands

Complexes of the formulae [(-Cp)Ru(PPh3)(2-PPH)]Cl and [(Cp)Ru(PPh3) (py)(1-PPH)]Cl were prepared by reacting pyridyl-2-phenylhydrazone [PPH, C5H4N-2-CH=NNHPh] with (-Cp)Ru(PPh3)2Cl and (-Cp)Ru(PPh3)(py)Cl, respectively. In these complexes the PPH ligand displays bidentate chelating and unidentate modes of bonding. The molecular structure of [(-Cp)Ru(PPh3)(2-PPH)](ClO4)·CH2Cl2 was determined by X-ray crystallography. In this complex the metal is bonded to the N-pyridyl and N-imine atoms of the chelating ligand. 1H NMR spectral data suggests that PPH is bonded to ruthenium through the pyridine moiety of the PPH ligand in [(η-Cp)Ru(PPh3)(py)(η1-PPH)]Cl.

Assignment of Fundamental Vibrations of Hydrazo Derivatives. Carbohydrazide and Diprotonated Carbohydrazide

The Infrared spectra of carbohydrazide, diprotonated carbohydrazide and their deuterated compounds have been measured in the solid state. From the results on thio- and selenocarbohydrazides and other related molecules and normal coordinate analyses using a Urey-Bradley force field assignments of the fundamental vibrational frequencies and a description of the normal modes of carbohydrazide, diprotonated carbohydrazide and their deuterated species are given.