Intrinsic dielectric response in ferroelectric nano-capacitors

Measurements on 'free-standing' single-crystal barium titanate capacitors with thickness down to 75 nm show a dielectric response typical of large single crystals, rather than conventional thin films. There is a notable absence of any broadening or temperature shift of the dielectric peak or loss tangent. Peak dielectric constants of similar to25 000 are observed, and Curie-Weiss analysis demonstrates first order transformation behaviour. This is in dramatic contrast to results on conventionally deposited thin film capacitor heterostructures, which show large dielectric peak broadening and temperature shifts (e.g. Parker et al 2002 Appl. Phys. Lett. 81 340), as well as an apparent change in the nature-of the paraelectric-ferroelectric transition from first to second order. Our data are compatible with a recent model by Bratkovsky and Levanyuk (2004 Preprint cond-mat/0402100), which attributes dielectric peak broadening to gradient terms that will exist in any thin film capacitor heterostructure. The observed recovery of first order transformation behaviour is consistent with the absence of significant substrate clamping in our experiment, as modelled by Pertsev et al (1998,Phys. Rev. Lett. 80 1988), and illustrates that the second order behaviour seen in conventionally deposited thin films cannot be attributed to the effects of reduced dimensionality in the system, nor to the influence of an intrinsic universal interfacial capacitance associated with the electrode- ferroelectric interface.

Magnetic tight binding and the iron-chromium enthalpy anomaly

We describe a self-consistent magnetic tight-binding theory based in an expansion of the Hohenberg-Kohn density functional to second order, about a non-spin-polarized reference density. We show how a first order expansion about a density having a trial input magnetic moment leads to a fixed moment model. We employ a simple set of tight-binding parameters that accurately describes electronic structure and energetics, and show these to be transferable between first row transition metals and their alloys. We make a number of calculations of the electronic structure of dilute Cr impurities in Fe, which we compare with results using the local spin density approximation. The fixed moment model provides a powerful means for interpreting complex magnetic configurations in alloys; using this approach, we are able to advance a simple and readily understood explanation for the observed anomaly in the enthalpy of mixing.

Comparative study of diastereoisomer interconversion in chiral BINOL-ate and diamine platinum complexes of conformationally flexible NUPHOS diphosphines

A thorough and detailed study of diastereointerconversion in the chiral platinum complexes [(NUPHOS)Pt{(S)-BINOL}] (3a-e) has been undertaken and compared with the results of a similar study with [(BIPHEP)Pt{(S)-BINOL}]. Rate data revealed that this process obeys first-order relaxation kinetics, and rate constants for conversion of the minor to the major diastereoisomer have been obtained. Eyring analysis of the data gave DeltaH(double dagger) and DeltaS(double dagger) values of 22-25 kcal mol(-1) and -1 to -16 eu, respectively. In combination with computational analysis, these studies indicate that atropinversion most likely occurs via an on-metal pathway involving a planar seven-membered transition state. Substitution of (S)-BINOL for (S,S)-DPEN results in a marked reduction in the barrier to atropinversion; a DeltaH(double dagger) value of 17 kcal mol(-1) has been determined for the conversion of delta-[(Ph-4-NUPHOS)Pt{(S,S)-DPEN}]Cl-2 to lambda-[(Ph-4-NUPHOS)Pt{(S,S)-DPEN}]Cl-2, which could indicate that an alternative mechanism operates.

Melting of a tetrahedral network model of silica

Thermal properties of an idealised tetrahedral network model of silica are investigated by Monte Carlo simulations. The interatomic potential consists of anharmonic stretching and bending terms, plus a short range repulsion. The model includes a bond interchange rule similar to the well known Wooten, Winer and Weaire (WWW) algorithm (see Phys. Rev. Lett., 1985, 54, 1392). Simulations reveal an apparent first order melting transition at T = 2200 K. The computed changes in the local coordination upon melting are consistent with experimental and ab initio data.

Second-order NMR spectra at high field of common organic functional groups

The proton NMR spectra of aryl n-propyl sulfides gave rise to what may appear to be first-order proton NMR spectra. Upon oxidation to the corresponding sulfone, the spectra changed appearance dramatically and were clearly second-order. A detailed analysis of these second-order spectra, in the sulfone series, provided vicinal coupling constants which indicated that these compounds had a moderate preference for the anti-conformer, reflecting the much greater size of the sulfone over the sulfide. It also emerged, from this study, that the criterion for observing large second-order effects in the proton NMR spectra of 1,2-disubstituted ethanes was that the difference in vicinal coupling constants must be large and the difference in geminal coupling constants must be small. n-Propyl triphenylphosphonium bromide and 2-trimethylsilylethanesulfonyl chloride, and derivatives thereof, also exhibited second-order spectra, again due to the bulky substituents. Since these spectra are second-order due to magnetic nonequivalence of the nuclei in question, not chemical shifts, the proton spectra are perpetually second-order and can never be rendered first-order by using higher field NMR spectrometers.

The interactions of coal with CO2 and its effects on coal structure

The interactions of coal with CO2 at pressures of up to 30 bar concerning mechanisms of diffusion, the strength of interactions, and the irreversibility of uptake for the permanent disposal of CO2 into coal fields have been studied. Differential scanning calorimetry was used to investigate coal/CO2 interactions for North Dakota, Wyodak, Illinois No. 6, and Pittsburgh No. 8 coals. It was found that the first interactions of CO2 with coals led to strongly bound carbon dioxide on coal. Energy values attributed to the irreversible storage capacity for CO2 on coals were determined. The lowest irreversible sorption energy was found for North Dakota coal (0.44 J/g), and the highest value was for the Illinois No. 6 coal (8.93 J/g). The effect of high-pressure CO2 on the macromolecular structure of coal was also studied by means of differential scanning calorimetry. It was found that the temperature of the second-order phase transition of Wyodak coal decreases with an increase in CO2 pressure significantly, indicating that high-pressure CO2 diffuses through the coal matrix, causes significant plasticization effects, and changes the macromolecular structure of the Wyodak coal. Desorption characteristics of CO2 from the Pittsburgh No. 8 coal were studied by temperature-programmed desorption mass spectrometry. It was found that CO2 desorption from the coal is an activated process and follows a first-order kinetic model. The activation energy for CO2 desorption from the Pittsburgh No. 8 coal increased with the preadsorbed CO2 pressure, indicating that CO2 binds more strongly and demands more energy to desorb from the Pittsburgh No. 8 coal at higher pressures.

Thermodynamical studies of irreversible sorption of CO2 by Wyodak coal

Differential scanning calorimetry (DSC), temperature programmed desorption mass spectrometry (TPD-MS) and small angle neutron scattering (SANS) were used to investigate CO2 uptake by the Wyodak coal. The adsorption of carbon dioxide on Wyodak coal was studied by DSC. The exotherms evident at low temperatures are associated with the uptake of CO2 suggesting that carbon dioxide interacts strongly with the coal surface. The reduction in the value of the exotherms between the first and second runs for the Wyodak coal suggests that some CO2 is irreversibly bound to the structure even after heating to 200 °C DSC results also showed that adsorption of CO2 on the coal surface is an activated process and presumably at the temperature of the exotherms there is enough thermal energy to overcome the activation energy for adsorption. The adsorption process is instantly pursued by much slower diffusion of the gas molecules into the coal matrix (absorption). Structural rearrangement in coal by CO2 is examined by change in the glass transition temperature of coal after CO2 uptake at different pressures. The amount of gas dissolved in the coal increases with increasing CO2 pressure. TPD-MS showed that CO2 desorption from the Wyodak coal follows a first order kinetic model. Increase in the activation energy for desorption with pre-adsorbed CO2 pressure suggests that higher pressures facilitate the transport of CO2 molecules through the barriers therefore the amount of CO2 uptake by the coal is greater at higher pressures and more attempts are required to desorb CO2 molecules sorbed at elevated pressures. These conclusions were further confirmed by examining the Wyodak coal structure in high pressure CO 2 by SANS.

Emission lines of Fe XI in the 257-407 A wavelength region observed in solar spectra from EIS/Hinode and SERTS

Theoretical emission-line ratios involving Fe xi transitions in the 257-407 A wavelength range are derived using fully relativistic calculations of radiative rates and electron impact excitation cross-sections. These are subsequently compared with both long wavelength channel Extreme-Ultraviolet Imaging Spectrometer (EIS) spectra from the Hinode satellite (covering 245-291 A) and first-order observations (similar to 235-449 A) obtained by the Solar Extreme-ultraviolet Research Telescope and Spectrograph (SERTS). The 266.39, 266.60 and 276.36 A lines of Fe xi are detected in two EIS spectra, confirming earlier identifications of these features, and 276.36 A is found to provide an electron density (N-e) diagnostic when ratioed against the 257.55 A transition. Agreement between theory and observation is found to be generally good for the SERTS data sets, with discrepancies normally being due to known line blends, while the 257.55 A feature is detected for the first time in SERTS spectra. The most useful Fe xi electron density diagnostic is found to be the 308.54/352.67 intensity ratio, which varies by a factor of 8.4 between N-e = 108 and 1011 cm-3, while showing little temperature sensitivity. However, the 349.04/352.67 ratio potentially provides a superior diagnostic, as it involves lines which are closer in wavelength, and varies by a factor of 14.7 between N-e = 108 and 1011 cm-3. Unfortunately, the 349.04 A line is relatively weak, and also blended with the second-order Fe x 174.52 A feature, unless the first-order instrument response is enhanced.

Alkaline hydrolysis of trinitrotoluene, TNT

The kinetics of the alkaline hydrolysis of trinitrotoluene, TNT, in an aqueous solution is a possible approach to destroying the active agent in unwanted munitions. The kinetics are shown to have a rapid initial step, step A, in which a highly coloured species, X (lambda(max) = 450 nm) is formed via an equilibrium reaction: TNT + OH- double left right arrow X. The bimolecular rate constant for the forward part of this equilibrium process, k(1), is: 0.099 +/- 0.004, 0.32 +/- 0.02 and 1.27 +/- 0.05 dm(3) mol(-1) s(-1), at 25, 40 and 60degreesC, respectively. The activation energy for the forward process is 60 kJ mol(-1). The first-order rate constant for the reverse of this process, k(-1), is: (5.3 +/- 2.6) x 10(-4), (1.2 +/- 1.0) x 10(-3) and (7.7 +/- 2.9) x 10(-3) s(-1) at 25, 40 and 60degreesC, respectively. The activation energy for the overall equilibrium process (k(1)/k(-1)) is ca. -5 kJ mol(-1). The subsequent alkaline hydrolysis of X to form the final product P, i.e. step B, is much slower than step A and appears to comprise two processes coupled in series, i.e. steps B1 (X +2OH(-) --> Z) and B2 (Z+OH- --> P). At 25degreesC, Step B1 appears rate determining throughout the decay process. At 45 degreesC and, more so, at 60degreesC, step B appears increasingly biphasic with increasing alkaline concentrations, as step B2 begins to compete with step B1 for position as the rate determining step. The trimolecular rate constant for step B1 is: 0.017 +/- 0.001, 0.0085 +/- 0.0002 and 0.0011 +/- 0.0001 dm(6) mol(-2) s(-1) at 25, 40 and 60degreesC, respectively, and the process has an activation energy of 64 kJ mol(-1). The transition from uniform kinetics, described by step B1, to mixed kinetics, described by steps B1 and B2, as the reaction temperature and alkali concentration are increased most likely occurs because (a) step B2 has a lower activation energy than B1, although it was not possible to measure the former parameter, and (b) step B2 has a lower (1st) order dependence upon [OH-] compared with that of step B1 (2nd). The bimolecular rate constant for step B2 is 0.0035 +/- 0.03 dm(3) mol(-1) s(-1) at 60degreesC. A brief NMR study of the initial hydrolysis product in water, acetone and chloroform, coupled with UV/visible spectra, provides evidence that species X is a Meisenheimer complex.

Changing attitudes to gender roles: A longitudinal analysis of ordinal response data from the British household panel study

This article examines changes in attitudes to gender roles in contemporary Britain by using a first-order Markov process in which cumulative transition probabilities are logistic functions of a set of personal and socioeconomic characteristics of respondents. The data are taken from the British Household Panel Study (BHPS). The attitudinal responses examined take the form of ordinal responses concerning gender roles in 1991 and 2003. The likelihood function is partitioned to make possible the use of existing software for estimating model parameters. For the BHPS data, it was found that, depending on the value of the response in 1991, a variety of factors were important determinants of attitudes to gender roles by 2003.

Kinetics of levoglucosan and formaldehyde formation during cellulose pyrolysis process

The mechanisms and kinetics studies of the formation of levoglucosan and formaldehyde from anhydroglucose radical have been carried out theoretically in this paper. The geometries and frequencies of all the stationary points are calculated at the B3LYP/6-31+G(D,P) level based on quantum mechanics, Six elementary reactions are found, and three global reactions are involved. The variational transition-state rate constants for the elementary reactions are calculated within 450-1500 K. The global rate constants for every pathway are evaluated from the sum of the individual elementary reaction rate constants. The first-order Arrhenius expressions for these six elementary reactions and the three pathways are suggested. By comparing with the experimental data, computational methods without tunneling correction give good description for Path1 (the formation of levoglucosan); while methods with tunneling correction (zero-curvature tunneling and small-curvature tunneling correction) give good results for Path2 (the first possibility for the formation of formaldehyde), all the test methods give similar results for Path3 (the second possibility for the formation of formaldehyde), all the modeling results for Path3 are in good agreement with the experimental data, verifying that it is the most possible way for the formation of formaldehyde during cellulose pyrolysis. © 2012 Elsevier Ltd. All rights reserved.

Kinetics study on thermal dissociation of levoglucosan during cellulose pyrolysis

(Chemical Equation Presented) The mechanisms and kinetics studies of the levoglucosan (LG) primary decomposition during cellulose pyrolysis have been carried out theoretically in this paper. Three decomposition mechanisms (C-O bond scission, C-C bond scission, and LG dehydration) including nine pathways and 16 elementary reactions were studied at the B3LYP/6-31 + G(D,P) level based on quantum mechanics. The variational transi-tion- state rate constants for every elementary reaction and every pathway were calculated within 298-1550 K. The first-order Arrhenius expressions for these 16 elementary reactions and nine pathways were suggested. It was concluded that computational method using transition state theory (TST) without tunneling correction gives good description for LG decomposition by comparing with the experimental result. With the temperature range of 667-1327 K, one dehydration pathway, with one water molecule composed of a hydrogen atom from C3 and a hydroxyl group from C2, is a preferred LG decomposition pathway by fitting well with the experimental results. The calculated Arrhenius plot of C-O bond scission mechanism is better agreed with the experimental Arrhenius plot than that of C-C bond scission. This C-O bond scission mechanism starts with breaking of C1-O5 and C6-O1 bonds with formation of CO molecule (C1-O1) simultaneously. C-C bond scission mechanism is the highest energetic barrier pathway for LG decomposition. © 2013 Elsevier Ltd. All rights reserved.

Blind Characterisation of Sensors with Second-Order Dynamic Response

Compensation for the dynamic response of a temperature sensor usually involves the estimation of its input on the basis of the measured output and model parameters. In the case of temperature measurement, the sensor dynamic response is strongly dependent on the measurement environment and fluid velocity. Estimation of time-varying sensor model parameters therefore requires continuous textit{in situ} identification. This can be achieved by employing two sensors with different dynamic properties, and exploiting structural redundancy to deduce the sensor models from the resulting data streams. Most existing approaches to this problem assume first-order sensor dynamics. In practice, however second-order models are more reflective of the dynamics of real temperature sensors, particularly when they are encased in a protective sheath. As such, this paper presents a novel difference equation approach to solving the blind identification problem for sensors with second-order models. The approach is based on estimating an auxiliary ARX model whose parameters are related to the desired sensor model parameters through a set of coupled non-linear algebraic equations. The ARX model can be estimated using conventional system identification techniques and the non-linear equations can be solved analytically to yield estimates of the sensor models. Simulation results are presented to demonstrate the efficiency of the proposed approach under various input and parameter conditions.

Higher order derivatives and norms of certain matrix functions

Tese de doutoramento, Matemática (Álgebra Lógica e Fundamentos), Universidade de Lisboa, Faculdade de Ciências, 2014

Effective-fourth-order resonator based MASH bandpass sigma-delta modulators

Two novel effective-fourth-order (eighth-order) resonator based MASH (MultistAge noise SHaping) bandpass Σ-Δ modulators are introduced at the behavioural level and subsequently examined by simulations utilising the ALTA SPW environment. The considered bandpass configurations have in their loop filter a cascade of standard second-order resonator structures in order to achieve appropriate noise shaping. The quantisation noise in each stage is suppressed by feeding the error of each section into the input of the following stage. It is demonstrated in this paper that the quadruple effective-first-order cascade configuration has significantly better performance as well as conforming more closely with theory in comparison with the effective-second-order effective-second-order cascade. The superior performance of the former can be attributed to the cumulative effect of the multi-bit outputs as well as the presence of more notch filters.