SIMULATION OF THE OXYGEN-ATOM VACANCY IN THE HIGH-TEMPERATURE SUPERCONDUCTOR TIBA2CAN-1CUNO2N+2.5(N = 1)

These simulation calculations for the oxygen-atom vacancy in the high temperature superconductor TlBa2Ca(n-1)Cu(n)O2n+2.5(n = 1) have been performed by means of the tight-binding approximation based on the EHMO method. The results indicate that the effect of the oxygen-atom vacancy on the charge distributions at the Tl-, Ba-, Cu- and O-atom sites is appreciably different and that there may exist two kinds of Cu cation with different net charges (approximately + 3.0 or approximately + 1.0) due to the oxygen-atom vacancy in the lattice. The electric field gradient at the site of the oxygen-atom vacancy has been calculated. The position of the oxygen-atom vacancy which favours the high temperature superconductivity of TlBa2Ca(n-1)Cu(n)O2n+2.5(n = 1) has been discussed.

Bridge-vehicle interaction for structural health monitoring: potentials, applications, and limitations

Structural Health Monitoring (SHM) is an integral part of infrastructure maintenance and management systems due to socio-economic, safety and security reasons. The behaviour of a structure under vibration depends on structure characteristics. The change of structure characteristics may suggest the change in system behaviour due to the presence of damage(s) within. Therefore the consistent, output signal guided, and system dependable markers would be convenient tool for the online monitoring, the maintenance, rehabilitation strategies, and optimized decision making policies as required by the engineers, owners, managers, and the users from both safety and serviceability aspects. SHM has a very significant advantage over traditional investigations where tangible and intangible costs of a very high degree are often incurred due to the disruption of service. Additionally, SHM through bridge-vehicle interaction opens up opportunities for continuous tracking of the condition of the structure. Research in this area is still in initial stage and is extremely promising. This PhD focuses on using bridge-vehicle interaction response for SHM of damaged or deteriorating bridges to monitor or assess them under operating conditions. In the present study, a number of damage detection markers have been investigated and proposed in order to identify the existence, location, and the extent of an open crack in the structure. The theoretical and experimental investigation has been conducted on Single Degree of Freedom linear system, simply supported beams. The novel Delay Vector Variance (DVV) methodology has been employed for characterization of structural behaviour by time-domain response analysis. Also, the analysis of responses of actual bridges using DVV method has been for the first time employed for this kind of investigation.

High-sensitivity rod photoreceptor input to the blue-yellow color opponent pathway in macaque retina.

Small bistratified cells (SBCs) in the primate retina carry a major blue-yellow opponent signal to the brain. We found that SBCs also carry signals from rod photoreceptors, with the same sign as S cone input. SBCs exhibited robust responses under low scotopic conditions. Physiological and anatomical experiments indicated that this rod input arose from the AII amacrine cell-mediated rod pathway. Rod and cone signals were both present in SBCs at mesopic light levels. These findings have three implications. First, more retinal circuits may multiplex rod and cone signals than were previously thought to, efficiently exploiting the limited number of optic nerve fibers. Second, signals from AII amacrine cells may diverge to most or all of the approximately 20 retinal ganglion cell types in the peripheral primate retina. Third, rod input to SBCs may be the substrate for behavioral biases toward perception of blue at mesopic light levels.

Interpolation formula between very low and intermediate-to-high damping Kramers escape rates for single-domain ferromagnetic particles

It is shown that the Mel'nikov-Meshkov formalism for bridging the very low damping (VLD) and intermediate-to-high damping (IHD) Kramers escape rates as a function of the dissipation parameter for mechanical particles may be extended to the rotational Brownian motion of magnetic dipole moments of single-domain ferromagnetic particles in nonaxially symmetric potentials of the magnetocrystalline anisotropy so that both regimes of damping, occur. The procedure is illustrated by considering the particular nonaxially symmetric problem of superparamagnetic particles possessing uniaxial anisotropy subject to an external uniform field applied at an angle to the easy axis of magnetization. Here the Mel'nikov-Meshkov treatment is found to be in good agreement with an exact calculation of the smallest eigenvalue of Brown's Fokker-Planck equation, provided the external field is large enough to ensure significant departure from axial symmetry, so that the VLD and IHD formulas for escape rates of magnetic dipoles for nonaxially symmetric potentials are valid.

On the required shape corrections to the local density and generalized gradient approximations to the Kohn-Sham potentials for molecular response calculations of (hyper)polarizabilities and excitation energies

It is well known that shape corrections have to be applied to the local-density (LDA) and generalized gradient (GGA) approximations to the Kohn-Sham exchange-correlation potential in order to obtain reliable response properties in time dependent density functional theory calculations. Here we demonstrate that it is an oversimplified view that these shape corrections concern primarily the asymptotic part of the potential, and that they affect only Rydberg type transitions. The performance is assessed of two shape-corrected Kohn-Sham potentials, the gradient-regulated asymptotic connection procedure applied to the Becke-Perdew potential (BP-GRAC) and the statistical averaging of (model) orbital potentials (SAOP), versus LDA and GGA potentials, in molecular response calculations of the static average polarizability alpha, the Cauchy coefficient S-4, and the static average hyperpolarizability beta. The nature of the distortions of the LDA/GGA potentials is highlighted and it is shown that they introduce many spurious excited states at too low energy which may mix with valence excited states, resulting in wrong excited state compositions. They also lead to wrong oscillator strengths and thus to a wrong spectral structure of properties like the polarizability. LDA, Becke-Lee-Yang-Parr (BLYP), and Becke-Perdew (BP) characteristically underestimate contributions to alpha and S-4 from bound Rydberg-type states and overestimate those from the continuum. Cancellation of the errors in these contributions occasionally produces fortuitously good results. The distortions of the LDA, BLYP, and BP spectra are related to the deficiencies of the LDA/GGA potentials in both the bulk and outer molecular regions. In contrast, both SAOP and BP-GRAC potentials produce high quality polarizabilities for 21 molecules and also reliable Cauchy moments and hyperpolarizabilities for the selected molecules. The analysis for the N-2 molecule shows, that both SAOP and BP-GRAC yield reliable energies omega(i) and oscillator strengths f(i) of individual excitations, so that they reproduce well the spectral structure of alpha and S-4.(C) 2002 American Institute of Physics.

Shape corrections to exchange-correlation potentials by gradient-regulated seamless connection of model potentials for inner and outer region

Shape corrections to the standard approximate Kohn-Sham exchange-correlation (xc) potentials are considered with the aim to improve the excitation energies (especially for higher excitations) calculated with time-dependent density functional perturbation theory. A scheme of gradient-regulated connection (GRAC) of inner to outer parts of a model potential is developed. Asymptotic corrections based either on the potential of Fermi and Amaldi or van Leeuwen and Baerends (LB) are seamlessly connected to the (shifted) xc potential of Becke and Perdew (BP) with the GRAC procedure, and are employed to calculate the vertical excitation energies of the prototype molecules N-2, CO, CH2O, C2H4, C5NH5, C6H6, Li-2, Na-2, K-2. The results are compared with those of the alternative interpolation scheme of Tozer and Handy as well as with the results of the potential obtained with the statistical averaging of (model) orbital potentials. Various asymptotically corrected potentials produce high quality excitation energies, which in quite a few cases approach the benchmark accuracy of 0.1 eV for the electronic spectra. Based on these results, the potential BP-GRAC-LB is proposed for molecular response calculations, which is a smooth potential and a genuine "local" density functional with an analytical representation. (C) 2001 American Institute of Physics.

Azepanium-based ionic liquids as green electrolytes for high voltage supercapacitors

This work provides a first-time-study of Azepanium-based ionic liquids (ILs) as electrolyte components for electrochemical double layer capacitors (EDLCs). Herein, two Azepanium-based ILs, namely N-methyl, N-butyl-azepanium bis(trifluoromethanesulfonyl)imide (Azp(14)TFSI) and N-methyl, N-hexyl-azepanium bis(trifluoromethanesulfonyl)imide (Azp(16)TFSI) were compared with the established IL N-butyl, N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr(14)TFSI) in terms of viscosity, conductivity, thermal stability and electrochemical behavior in EDLC systems. The ILs' operative potentials were found to be comparable, leading to operative voltages up to 3.5 V without significant electrolyte degradation. 

Mixtures of azepanium based ionic liquids and propylene carbonate as high voltage electrolytes for supercapacitors

This work provides a study of mixtures of the azepanium-based ionic liquid (IL) N-methyl, N-butyl-azepanium bis[(trifluoromethane) sulfonyl]imide (Azp₁₄TFSI) and propylene carbonate (PC) as electrolyte components in electrochemical double layer capacitors (EDLCs). The considered mixtures' properties were then compared to the properties of mixtures of N-butyl, N-methylpyrrolidinium bis[(trifluoromethane) sulfonyl]imide (Pyr₁₄TFSI) and PC in terms of viscosity, conductivity and electrochemical behavior. The mixtures' operative potentials were found to be comparable to each other, leading to operative voltages as high as 3.5 V, while retaining the low viscosities and high conductivities of PC based EDLC electrolytes.

High temperature vapour-liquid equilibria of water-polyalcohol mixtures

Tese de doutoramento, Química (Química Tecnológica), Universidade de Lisboa, Faculdade de Ciências, 2014

Phonon spectra and thermodynamic properties of rare gas solids based on empirical and semi-empirical (ab initio) two-body potentials : a comparative study /

We study the phonon dispersion, cohesive and thermal properties of raxe gas solids Ne, Ar, Kr, and Xe, using a variety of potentials obtained from different approaches; such as, fitting to crystal properties, purely ab initio calculations for molecules and dimers or ab initio calculations for solid crystalline phase, a combination of ab initio calculations and fitting to either gas phase data or sohd state properties. We explore whether potentials derived with a certain approaxih have any obvious benefit over the others in reproducing the solid state properties. In particular, we study phonon dispersion, isothermal ajid adiabatic bulk moduli, thermal expansion, and elastic (shear) constants as a function of temperatiue. Anharmonic effects on thermal expansion, specific heat, and bulk moduli have been studied using A^ perturbation theory in the high temperature limit using the neaxest-neighbor central force (nncf) model as developed by Shukla and MacDonald [4]. In our study, we find that potentials based on fitting to the crystal properties have some advantage, particularly for Kr and Xe, in terms of reproducing the thermodynamic properties over an extended range of temperatiures, but agreement with the phonon frequencies with the measured values is not guaranteed. For the lighter element Ne, the LJ potential which is based on fitting to the gas phase data produces best results for the thermodynamic properties; however, the Eggenberger potential for Ne, where the potential is based on combining ab initio quantum chemical calculations and molecular dynamics simulations, produces results that have better agreement with the measured dispersion, and elastic (shear) values. For At, the Morse-type potential, which is based on M0ller-Plesset perturbation theory to fourth order (MP4) ab initio calculations, yields the best results for the thermodynamic properties, elastic (shear) constants, and the phonon dispersion curves.

Temperature dependent high-resolution infrared photoabsorption cross-sections of trifluoromethyl sulphur pentafluoride

Absolute infrared photoabsorption cross-sections have been measured over the range 600-1500 cm(-1) for the powerful greenhouse gas SF5CF3 at high resolution (0.03 cm(-1)) and at temperatures between 203 and 298 K. Our data indicate that the integrated absorption intensity shows a weak negative dependence on temperature. It is concluded therefore that previous calculations of radiative forcings and global warming potentials based on room-temperature data are reasonable estimates for the atmosphere, but may be low by a few percent. (C) 2002 Elsevier Science B.V. All rights reserved.

Generative topographic mapping applied to clustering and visualization of motor unit action potentials

The identification and visualization of clusters formed by motor unit action potentials (MUAPs) is an essential step in investigations seeking to explain the control of the neuromuscular system. This work introduces the generative topographic mapping (GTM), a novel machine learning tool, for clustering of MUAPs, and also it extends the GTM technique to provide a way of visualizing MUAPs. The performance of GTM was compared to that of three other clustering methods: the self-organizing map (SOM), a Gaussian mixture model (GMM), and the neural-gas network (NGN). The results, based on the study of experimental MUAPs, showed that the rate of success of both GTM and SOM outperformed that of GMM and NGN, and also that GTM may in practice be used as a principled alternative to the SOM in the study of MUAPs. A visualization tool, which we called GTM grid, was devised for visualization of MUAPs lying in a high-dimensional space. The visualization provided by the GTM grid was compared to that obtained from principal component analysis (PCA). (c) 2005 Elsevier Ireland Ltd. All rights reserved.

Reduced cortico-motor facilitation in a normal sample with high traits of autism

Recent research in social neuroscience proposes a link between mirror neuron system (MNS) and social cognition. The MNS has been proposed to be the neural mechanism underlying action recognition and intention understanding and more broadly social cognition. Pre-motor MNS has been suggested to modulate the motor cortex during action observation. This modulation results in an enhanced cortico-motor excitability reflected in increased motor evoked potentials (MEPs) at the muscle of interest during action observation. Anomalous MNS activity has been reported in the autistic population whose social skills are notably impaired. It is still an open question whether traits of autism in the normal population are linked to the MNS functioning. We measured TMS-induced MEPs in normal individuals with high and low traits of autism as measured by the autistic quotient (AQ), while observing videos of hand or mouth actions, static images of a hand or mouth or a blank screen. No differences were observed between the two while they observed a blank screen. However participants with low traits of autism showed significantly greater MEP amplitudes during observation of hand/mouth actions relative to static hand/mouth stimuli. In contrast, participants with high traits of autism did not show such a MEP amplitude difference between observation of actions and static stimuli. These results are discussed with reference to MNS functioning.

Global and regional temperature-change potentials for near-term climate forcers

We examine the climate effects of the emissions of near-term climate forcers (NTCFs) from 4 continental regions (East Asia, Europe, North America and South Asia) using radiative forcing from the task force on hemispheric transport of air pollution source-receptor global chemical transport model simulations. These simulations model the transport of 3 aerosol species (sulphate, particulate organic matter and black carbon) and 4 ozone precursors (methane, nitric oxides (NOx), volatile organic compounds and carbon monoxide). From the equilibrium radiative forcing results we calculate global climate metrics, global warming potentials (GWPs) and global temperature change potentials (GTPs) and show how these depend on emission region, and can vary as functions of time. For the aerosol species, the GWP(100) values are −37±12, −46±20, and 350±200 for SO2, POM and BC respectively for the direct effects only. The corresponding GTP(100) values are −5.2±2.4, −6.5±3.5, and 50±33. This analysis is further extended by examining the temperature-change impacts in 4 latitude bands. This shows that the latitudinal pattern of the temperature response to emissions of the NTCFs does not directly follow the pattern of the diagnosed radiative forcing. For instance temperatures in the Arctic latitudes are particularly sensitive to NTCF emissions in the northern mid-latitudes. At the 100-yr time horizon the ARTPs show NOx emissions can have a warming effect in the northern mid and high latitudes, but cooling in the tropics and Southern Hemisphere. The northern mid-latitude temperature response to northern mid-latitude emissions of most NTCFs is approximately twice as large as would be implied by the global average.

Spectral gap for Glauber type dynamics for a special class of potentials

We consider an equilibrium birth and death type process for a particle system in infinite volume, the latter is described by the space of all locally finite point configurations on Rd. These Glauber type dynamics are Markov processes constructed for pre-given reversible measures. A representation for the ``carré du champ'' and ``second carré du champ'' for the associate infinitesimal generators L are calculated in infinite volume and for a large class of functions in a generalized sense. The corresponding coercivity identity is derived and explicit sufficient conditions for the appearance and bounds for the size of the spectral gap of L are given. These techniques are applied to Glauber dynamics associated to Gibbs measure and conditions are derived extending all previous known results and, in particular, potentials with negative parts can now be treated. The high temperature regime is extended essentially and potentials with non-trivial negative part can be included. Furthermore, a special class of potentials is defined for which the size of the spectral gap is as least as large as for the free system and, surprisingly, the spectral gap is independent of the activity. This type of potentials should not show any phase transition for a given temperature at any activity.