On the semiclassical approach to cold atomic collisions

We extend the semiclassical description of two-state atomic collisions to low energies for which the impact parameter treatment fails. The problem reduces to solving a system of first-order differential equations with coefficients whose semiclassical asymptotes experience the Stokes phenomenon in the complex coordinate plane. Primitive semiclassical and uniform Airy approximations are discussed.

An exactly solvable four transition point model

Heavy particle collisions, in particular low-energy ion-atom collisions, are amenable to semiclassical JWKB phase integral analysis in the complex plane of the internuclear separation. Analytic continuation in this plane requires due attention to the Stokes phenomenon which parametrizes the physical mechanisms of curve crossing, non-crossing, the hybrid Nikitin model, rotational coupling and predissociation. Complex transition points represent adiabatic degeneracies. In the case of two or more such points, the Stokes constants may only be completely determined by resort to the so-called comparison- equation method involving, in particular, parabolic cylinder functions or Whittaker functions and their strong-coupling asymptotics. In particular, the Nikitin model is a two transition-point one-double-pole problem in each half-plane corresponding to either ingoing or outgoing waves. When the four transition points are closely clustered, new techniques are required to determine Stokes constants. However, such investigations remain incomplete, A model problem is therefore solved exactly for scattering along a one-dimensional z-axis. The energy eigenvalue is b(2)-a(2) and the potential comprises -z(2)/2 (parabolic) and -a(2) + b(2)/2z(2) (centrifugal/centripetal) components. The square of the wavenumber has in the complex z-plane, four zeros each a transition point at z = +/-a +/- ib and has a double pole at z = 0. In cases (a) and (b), a and b are real and unitarity obtains. In case (a) the reflection and transition coefficients are parametrized by exponentials when a(2) + b(2) > 1/2. In case (b) they are parametrized by trigonometrics when a(2) + b(2) <1/2 and total reflection is achievable. In case (c) a and b are complex and in general unitarity is not achieved due to loss of flux to a continuum (O'Rourke and Crothers, 1992 Proc. R. Sec. 438 1). Nevertheless, case (c) coefficients reduce to (a) or (b) under appropriate limiting conditions. Setting z = ht, with h a real constant, an attempt is made to model a two-state collision problem modelled by a pair of coupled first-order impact parameter equations and an appropriate (T) over tilde-tau relation, where (T) over tilde is the Stueckelberg variable and tau is the reduced or scaled time. The attempt fails because (T) over tilde is an odd function of tau, which is unphysical in a real collision problem. However, it is pointed out that by applying the Kummer exponential model to each half-plane (O'Rourke and Crothers 1994 J. Phys. B: At. Mel. Opt. Phys. 27 2497) the current model is in effect extended to a collision problem with four transition points and a double pole in each half-plane. Moreover, the attempt in itself is not a complete failure since it is shown that the result is a perfect diabatic inelastic collision for a traceless Hamiltonian matrix, or at least when both diagonal elements are odd and the off-diagonal elements equal and even.

Equilibrium polymerization of cyclic carbonate oligomers

A model of the polymerization of ring oligomers of bisphenol A polycarbonate (BPA-PC) is used to investigate the influence of dimensionality (2D or 3D), density and temperature on the size distribution of the polymer chains. The polymerization step is catalyzed by a single active particle, conserves the number and type of the chemical bonds, and occurs without a significant gain in either potential energy or configurational entropy. Monte Carlo and molecular dynamics simulations show that polymerization of cyclic oligomers occurs readily at high density and is driven by the entropy associated with the distribution of interparticle bonds. Polymerization competes at lower densities with long range diffusion, which favors small molecular species, and is prevented if the system is sufficiently dilute. Polymerization occurs in 2D via a weakly first order transition as a function of density and is characterized by low hysteresis and large fluctuations in the size of polymer chains. Polymerization occurs more readily in 3D than in 2D, and is favored by increasing temperature, as expected for an entropy-driven process. (C) 2001 American Institute of Physics.

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.

Neighboring Group-Controlled Hydrolysis: Towards “Designer” Drug Release Biomaterials

To give the first demonstration of neighboring group-controlled drug delivery rates, a series of novel, polymerizable ester drug conjugates was synthesized and fully characterized. The monomers are suitable for copolymerization in biomaterials where control of drug release rate is critical to prophylaxis or obviation of infection. The incorporation of neighboring group moieties differing in nucleophilicity, geometry, and steric bulk in the conjugates allowed the rate of ester hydrolysis, and hence drug liberation, to be rationally and widely controlled. Solutions (2.5 x 10-5 mol dm-3) of ester conjugates of nalidixic acid incorporating pyridyl, amino, and phenyl neighboring groups hydrolyzed according to first-order kinetics, with rate constants between 3.00 ( 0.12 10-5 s -1 (fastest) and 4.50 ( 0.31 10- 6 s-1 (slowest). The hydrolysis was characterized using UV-visible spectroscopy. When copolymerized with poly(methyl methacrylate), free drug was shown to elute from the resulting materials, with the rate of release being controlled by the nature of the conjugate, as in solution. The controlled molecular architecture demonstrated by this system offers an attractive class of drug conjugate for the delivery of drugs from polymeric biomaterials such as bone cements in terms of both sustained, prolonged drug release and minimization of mechanical compromise as a result of release. We consider these results to be the rationale for the development of 'designer' drug release biomaterials, where the rate of required release can be controlled by predetermined molecular architecture.

Information used in detecting upcoming collisions.

In four experiments we examined the nature of the information used in judging whether events would or would not give rise to a collision in the near future. Observers were tested in situations depicting approaches between two objects (lateral approaches) and approaches between an object and the point of observation (head-on approaches), with objects moving according to constant deceleration or sinusoidal deceleration patterns. Judgments were found to be based, to a large extent, on the (in)sufficiency of current deceleration to avoid upcoming collision, as specified optically by tau-dot (tau over dot). However, the information specified, by tau (tau), that is the current (first-order) time remaining until contact, was also found to play a significant role. We deduce that judgment of upcoming collision is based on the detection Of T and its evolution over time, suggesting that observers are sensitive to Deltatau rather than to tau over dot itself.

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.

An investigation of possible mechanisms of the water-gas shift reaction over a ZrO2-supported Pt catalyst

The present work investigates the reactivity of the surface species observable by in situ DRIFTS formed over a Pt/ZrO2 during the water-gas shift (WGS) reaction. A DRIFTS cell/mass spectrometer system was operated at the chemical steady state during isotopic transients to yield information about the true nature (i.e., main reaction intermediate or spectators) of adsorbates. Only carbonyl and formate species were observed by DRIFTS under reaction conditions; the surface coverage of carbonate species was negligible. Isotopic transient kinetic analyses revealed that formates exchanged uniformly according to a first-order law, suggesting that most formates observed by DRIFTS were of the same reactivity. In addition, the time scale of the exchange of the reaction product CO2 was significantly shorter than that of the surface formates. Therefore, a formate route based on the formates as detected by DRIFTS can be ruled out as the main reaction pathway in the present case. The number of precursors of the reaction product CO2 was smaller than the number of surface Pt atoms, suggesting that carbonyl species or some \

An investigation of Fe XVI emission lines in solar and stellar extreme-ultraviolet and soft X-ray spectra

New fully relativistic calculations of radiative rates and electron impact excitation cross-sections for Fe XVI are used to determine theoretical emission-line ratios applicable to the 251-361 and 32-77 angstrom portions of the extreme-ultraviolet (EUV) and soft X-ray spectral regions, respectively. A comparison of the EUV results with observations from the Solar Extreme-Ultraviolet Research Telescope and Spectrograph (SERTS) reveals excellent agreement between theory and experiment. However, for emission lines in the 32-49 angstrom portion of the soft X-ray spectral region, there are large discrepancies between theory and measurement for both a solar flare spectrum obtained with the X-Ray Spectrometer/Spectrograph Telescope (XSST) and for observations of Capella from the Low- Energy Transmission Grating Spectrometer (LETGS) on the Chandra X-ray Observatory. These are probably due to blending in the solar flare and Capella data from both first-order lines and from shorter wavelength transitions detected in second and third order. By contrast, there is very good agreement between our theoretical results and the XSST and LETGS observations in the 50-77 angstrom wavelength range, contrary to previous results. In particular, there is no evidence that the Fe XVI emission from the XSST flare arises from plasma at a much higher temperature than that expected for Fe XVI in ionization equilibrium, as suggested by earlier work.

Unusual voltammetry of the reduction of O-2 in [C(4)dmim][N(Tf)(2)] reveals a strong interaction of O-2(center dot-) with the [C(4)dmim](+) cation

Voltammetric studies of the reduction of oxygen in the room temperature ionic liquid [C(4)dmim][N(Tf)(2)] have revealed a significant positive shift in the back peak potential, relative to that expected for a simple electron transfer. This shift is thought to be due to the strong association of the electrogenerated superoxide anion with the solvent cation. In this work we quantitatively simulate the microdisc electrode voltammetry using a model based upon a one-electron reduction followed by a reversible chemical step, involving the formation of the [C(4)dmim](+)center dot center dot center dot O-2(center dot-) ion-pair, and in doing so we extract a set of parameters completely describing the system. We have simulated the voltammetry in the absence of a following chemical step and have shown that it is impossible to simultaneously fit both the forward and reverse peaks. To further support the parameters extracted from fitting the experimental voltammetry, we have used these parameters to independently simulate the double step chronoamperometric response and found excellent agreement. The parameters used to describe the association of the O-2(center dot-) with the [C(4)dmim](+) were k(f) = 1.4 x 10(3) s(-1) for the first-order rate constant and K-eq = 25 for the equilibrium constant.

Size Effects on Thin Film Ferroelectrics: Experiments on Isolated Single Crystal Sheets

Thin lamellae were cut from bulk single crystal BaTiO3 using a Focused Ion Beam Microscope. They were then removed and transferred onto single crystal MgO substrates, so that their functional properties could be measured independent of the original host bulk ferroelectric. The temperature dependence of the capacitance of these isolated single crystal films was found to be strongly bulk-like, demonstrating a sharp Curie anomaly, as well as Curie-Weiss behaviour. In addition, the sudden change in the remanent polarisation as a function of temperature at TC was characteristic of a first order phase change. The work represents a dramatic improvement on that previously published by M. M. Saad, P. Baxter, R. M. Bowman, J. M. Gregg, F. D. Morrison & J. F. Scott, J. Phys: Cond. Matt., 16 L451-L456 (2004), as critical shortcomings in the original specimen geometry, involving potential signal contributions from bulk BaTiO3, have now been obviated. That the functional properties of single crystal thin film lamellae are comparable to bulk, and not like those of conventionally deposited heteroegenous thin film systems, has therefore been confirmed.

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.

Kinetics of the oxidation of methyl tert-butyl ether (MTBE) by potassium permanganate

The occurrence of the fuel oxygenate methyl tert-butyl ether (MTBE) in the environment has received considerable scientific attention. The pollutant is frequently found in the groundwater due to leaking of underground storage tanks or pipelines. Concentrations of more than several mg/L MTBE were detected in groundwater at several places in the US and Germany in the last few years. In situ chemical oxidation is a promising treatment method for MTBE-contaminated plumes. This research investigated the reaction kinetics for the oxidation of MTBE by permanganate. Batch tests demonstrated that the oxidation of MTBE by permanganate is second order overall and first order individually with respect to permanganate and MTBE. The second-order rate constant was 1.426 x 10(-6) L/mg/h. The influence of pH on the reaction rate was demonstrated to have no significant effect. However, the rate of MTBE oxidation by potassium permanganate is 2-3 orders of magnitude lower than of other advanced oxidation processes. The slower rates of MTBE oxidation by permanganate limit the applicability of this process for rapid MTBE cleanup strategies. However, permanganate oxidation of MTBE has potential for passive oxidation risk management strategies. (C) 2002 Elsevier Science Ltd. All rights reserved.

Steric effects in the selective hydrogenation of cinnamaldehyde to cinnamyl alcohol using an Ir/C catalyst

The liquid phase selective hydrogenation of cinnamaldehyde to cinnamyl alcohol has been carried out over a graphite-supported iridium catalyst. The effect of reaction parameters such as temperature, pressure, concentration of reactant, the effect of addition of product to the feed and pre-reduction of the catalyst were studied. In situ pre-reduction of the catalyst with hydrogen had a very significant enhancing effect on the conversion of cinnamaldehyde and selectivity of the catalyst to cinnamyl alcohol. Kinetic analysis of the pre-reduced catalyst showed that the reaction is zero order with respect to cinnamaldehyde and first order with respect to hydrogen. The reaction follows an Arrhenius behaviour with an activation energy of 37 kJ mol(-1). Detailed analysis of the reaction showed that hydrogenation of the C=C double bond to give hydrocinnamaldehyde predominantly occurred at low conversions of cinnamaldehyde (

Dilute acid hydrolysis of cellulose and cellulosic bio-waste using a microwave reactor system

The dilute acid hydrolysis of grass and cellulose with phosphoric acid was undertaken in a microwave reactor system. The experimental data and reaction kinetic analysis indicate that this is a potential process for cellulose and hemi-cellulose hydrolysis, due to a rapid hydrolysis reaction at moderate temperatures. The optimum conditions for grass hydrolysis were found to be 2.5% phosphoric acid at a temperature of 175 degrees C. It was found that sugar degradation occurred at acid concentrations greater than 2.5% (v/v) and temperatures greater than 175 degrees C. In a further series of experiments, the kinetics of dilute acid hydrolysis of cellulose was investigated varying phosphoric acid concentration and reaction temperatures. The experimental data indicate that the use of microwave technology can successfully facilitate dilute acid hydrolysis of cellulose allowing high yields of glucose in short reaction times. The optimum conditions gave a yield of 90% glucose. A pseudo-homogeneous consecutive first order reaction was assumed and the reaction rate constants were calculated as: k(1) = 0.0813 s(-1); k(2) = 0.0075 s(-1), which compare favourably with reaction rate constants found in conventional non-microwave reaction systems. The kinetic analysis would indicate that the primary advantages of employing microwave heating were to: achieve a high rate constant at moderate temperatures: and to prevent 'hot spot' formation within the reactor, which would have cause localised degradation of glucose.