Solvation dynamics of a charge bubble in water

A microscopic theory is used to calculate the solvation-time correlation function, (S(t)), of a light, non-stationary charge bubble in water. The calculated correlation function is found to be similar to the energy-time correlation function of a solvated electron. The ionic mobility of a charge bubble of the size of the hydrated electron is also calculated. It is found that the mobility of the charge plays a very important role in its own solvation.

Spin and charge density waves in the extended Hubbard model: A slave-boson approach

We use the extended Hubbard model to investigate the properties of the charge- and spin-density-wave phases in the presence of a nearest-neighbors repulsion term in the framework of the slave-boson technique. We show that, contrary to Hartree-Fock results, an instablity may occur for sufficiently high values of the Hubbard repulsion, both in the spin- and charge-density-wave phase, which makes the system discontinuously jump to a phase with a smaller or zero wave amplitude. The limits of applicability of our approach are discussed and our results are compared with previous numerical analysis. The phase diagram of the model at half-filling is determined.

The effect of constituent metal ions on the electrokinetics of chalcopyrite

Chalcopyrite in contact with water is thermodynamically unstable in the presence of oxygen. Oxidation of chalcopyrite may take place due to various factors, e.g., geological environment, mining/comminution, and storage. In this work oxidation of chalcopyrite has been investigated through interfacial electrokinetics. The characteristics of samples obtained from different geological locations as well as the effects of ageing and laboratory oxidation have been delineated. Variation of the solid-liquid ratio was found to have a significant effect on the zeta-potential characteristics of chalcopyrite. The role of constituent metal ions, namely copper and iron, has been studied in the absence and presence of externally added metal ions. The results indicated that the ratio of Cu/Fe on the surface of oxidized chalcopyrite determines the Stern layer potential and under appropriate solution chemistry conditions influences charge reversals. The mineral surfaces, thus, could be either copper-rich or iron-rich as reflected by a shift in pH(iep),,(s). The observed charge reversals have been explained on the basis of a model proposed by James and Healy. (C) 1997 Academic Press.

The nature of charge ordering in rare earth manganates and its strong dependence on the size of the A-site cations

Charge ordering in rare earth manganates of the type Ln(0.5)A(0.5)MnO(3) (Ln = rare earth, A = alkaline earth) is highly sensitive to the average radius of the A-site cations, [r(A)]. Tn the small [r(A)] regime (e.g., Y0.5Ca0.5MnO3), charge ordering occurs in the paramagnetic state, the transformation to an antiferromagnetic state occurring at still lower temperatures. At moderate [r(A)] values (e.g., Nd0.5Sr0.5MnO3), a ferromagnetic metallic state transforms to a charge-ordered antiferromagnetic state with cooling. These two distinct types of charge ordering and associated properties are explained in terms of the variation of the exchange couplings J(FM) and J(AFM) with [r(A)] and the invariance of the single-ion Jahn-Teller energy with [r(A)]. A qualitative temperature-[r(A)] phase diagram, consistent with the experimental observations, has been constructed to describe the properties of the manganates in the different [r(A)] regimes. (C) 1997 Academic Press.

The two-step positive temperature coefficient in resistance characteristics of n-(Ba,Pb)TiO3 ceramics created through inclusion of grain boundary modifier additives

Donor-doped n-(Ba,Pb)TiO3 polycrystalline ceramics exhibit distinctly two-step positive temperature coefficient of resistance (PTCR) characteristics when formulated with suitable combinations of B2O3 and Al2O3 as grain boundary modifiers by heterogeneous addition. B2O3 or Al2O3 when added singularly resulted in either steep or broad PTCR jumps respectively across the phase transition. The two-step PTCR is attributed to the activation of the acceptor states, created through B2O3 and Al2O3, for various temperature regimes above the Curie point (T-c). The changing pattern of trap states is evident from the presence of Ti4+-O--Al3+ type hole centres in the grain boundary layer regions, identified in the electron paramagnetic resonance (EPR) spectra. That charge redistribution occurs among the inter-band gap defect states on crossing the Curie temperature is substantiated by the temperature coefficient in the EPR results. Capacitance-voltage results clearly show that there is an increase in the density of trap states with the addition of B2O3 and Al2O3. The spread in energy values of these trap states is evident from the large change in barrier height (phi similar or equal to 0.25-0.6 eV) between 500 and 650 K.

Transformation of a laterally diverging boundary layer flow to a two-dimensional boundary layer flow

Laterally diverging boundary layer flow over a plate is shown to be reducible to a two-dimensional flow by modelling the diverging streamlines by a source flow.

Unsteady compressible boundary layer flow in the stagnation region of a sphere with a magnetic field

Abstract: An analysis is performed to study the unsteady compressible laminar boundary layer flow in the forward stagnation-point region of a sphere with a magnetic field applied normal, to the surface. We have considered the case where there is an initial steady state that is perturbed by the step change in the total enthalpy at the wall. The nonlinear coupled parabolic partial differential equations governing the flow and heat transfer have been solved numerically using a finite-difference scheme. The numerical results are presented, which show the temporal development of the boundary layer. The magnetic field in the presence of variable electrical conductivity causes an overshoot in the velocity profile. Also, when the total enthalpy at the wall is suddenly increased, there is a change in the direction of transfer of heat in a small interval of time.

Latitude variation of boundary layer height over Indian Ocean during pre- and First Field Phase (FFP-98) of INDOEX

This paper describes the results of the measurement of the Marine Boundary Layer (MBL) height from spectral analysis of the u and v components of the wind and from CLASS/radiosonde temperature profiles. The data were collected on ORV Sagar Kanya during the pre-INDOEX (27 December 1996 through 31 January 1997) and FFP-98 (18 February to 31 March 1998) over the latitude range 15 degrees N to 14 degrees S and 15 degrees N to 20 degrees S respectively. During the pre-INDOEX, the MBL heights gradually decrease from 2.5 km at 13 degrees N to around 500 to 600 m at 10 degrees S, Similar results are observed in the return track. The MBL heights (0.5 to 1 km) obtained during FFP-98 are less compared to those obtained during pre-INDOEX. The MBL heights during FFP-98 are less compared to the pre-INDOEX and are believed to be due to the presence of stratus, stratocumulus and cumulus clouds during the cruise period, compared to a relatively cloud free pre-INDOEX cruise.

Graphitic Carbon as Durable Cathode-Catalyst Support for PEFCs

Long-term deterioration in the performance of PEFCs is attributed largely to reduction in active area of the platinum catalyst at cathode, usually caused by carbon-support corrosion. It is found that the use of graphitic carbon as cathode-catalyst support enhances its long-term stability in relation to non-graphitic carbon. This is because graphitic-carbon-supported- Pt (Pt/GrC) cathodes exhibit higher resistance to carbon corrosion in-relation to non-graphitic-carbon-supported- Pt (Pt/Non-GrC) cathodes in PEFCs during accelerated stress test (AST) as evidenced by chronoamperometry and carbon dioxide studies. The corresponding change in electrochemical surface area (ESA), cell performance and charge-transfer resistance are monitored through cyclic voltammetry (CV), cell polarisation and impedance measurements, respectively. The degradation in performance of PEFC with Pt/GrC cathode is found to be around 10% after 70 h of AST as against 77% for Pt/Non-GrC cathode. It is noteworthy that Pt/GrC cathodes can withstand even up to 100 h of AST with nominal effect on their performance. Xray diffraction (XRD), Raman spectroscopy, transmission electron microscopy and cross-sectional field-emission scanning electron microscopy (FE-SEM) studies before and after AST suggest lesser deformation in catalyst layer and catalyst particles for Pt/GrC cathodes in relation to Pt/Non-GrC cathodes, reflecting that graphitic carbon-support resists carbon corrosion and helps mitigating aggregation of Pt-particles.

Halogen Bonding in 2,5-Dichloro-1,4-benzoquinone: Insights from Experimental and Theoretical Charge Density Analysis

Experimental charge density distribution in 2, 5-dichloro-1, 4-benzoquinone has been carried out using high resolution X-ray diffraction data at 90 K to quantitatively evaluate the nature of C-Cl center dot center dot center dot O=C halogen bond in molecular crystals. Additionally, the halogen bond is studied from geometrical point of view and the same has been visualized using Hirshfeld surface analysis. The obtained results from experimental charge density analysis are compared with periodic quantum calculations using B3LYP 6-31G(d,p) level of theory. The topological values at bond critical point, three-dimensional static deformation density features and electrostatic potential isosurfaces unequivocally establish the attractive nature of C-Cl center dot center dot center dot O=C halogen bond in crystalline lattice.

Mean-field theory of charge ordering and phase transitions in the colossal-magnetoresistive manganites

We study phase transitions in the colossal-magnetoresistive manganites by using a mean-field theory both at zero and non-zero temperatures. Our Hamiltonian includes double-exchange, superexchange, and Hubbard terms with on-site and nearest-neighbour Coulomb interaction, with the parameters estimated from earlier density-functional calculations. The phase diagrams show magnetic and charge-ordered (or charge-disordered) phases as a result of the competition between the double-exchange, superexchange, and Hubbard terms, the relative effects of which are sensitively dependent on parameters such as doping, bandwidth, and temperature. In accord with the experimental observations, several important features are reproduced from our model, namely, (i) a phase transition from an insulating, charge-ordered antiferromagnetic to a metallic, charge-disordered ferromagnetic state near dopant concentration x = 1/2, (ii) the reduction of the transition temperature TAF-->F by the application of a magnetic field, (iii) melting of the charge order by a magnetic field, and (iv) phase coexistence for certain values of temperature and doping. An important feature, not reproduced in our model, is the antiferromagnetism in the electron-doped systems, e.g., La1-xCaxMnO3 over the entire range of 0.5 less than or equal to x less than or equal to 1, and we suggest that a multi-band model which includes the unoccupied t(2g) orbitals might be an important ingredient for describing this feature.

Modulation of lifetimes and diastereomeric discrimination in triplet-excited substituted butane-1,4-diones through intramolecular charge-transfer quenching

Triplet lifetimes have been determined for the diastereomers of a broad set of butane-l,4-dione derivatives (1-3). A remarkable dependence of lifetimes on conformational preferences is revealed in that the lifetimes are shorter for the meso diastereomers of 1-3 than those for the racemic ones. The intramolecular beta-phenyl quenching is promoted in the case of meso diastereomers by virtue of the gauche relationship between the excited carbonyl group and the beta-aryl ring, while a distal arrangement in the lowest energy conformation (H-anti) in racemic diastereomers prevents such a deactivation. The involvement of charge transfer in the intramolecular beta-phenyl quenching is suggested by the correlation of the triplet lifetimes of the meso diastereomers of compounds 2 with the nature of the substituent on the beta-phenyl rings. In the case of racemic diastereomers, beta-methoxy substitution on the beta-phenyl ring (2-OCH3, 3-OCH3) also led to a decrease of the triplet lifetimes when compared to those of the nonsubstituted compounds (2-H, 3-H). This shortening is accounted for by the deactivation of a small proportion of the excited molecules through beta-phenyl quenching. In addition to the above factors, the lifetimes in the case of meso diastereomers can further be controlled by increasing the energy spacing between the T-1 and T-2 states, since beta-phenyl quenching occurs from the latter for compounds 2 and 3. Through a rational conformational control, a surprisingly long triplet lifetime (300 ns) has been measured for the first time for a purely n,pi* triplet-excited beta-phenylpropiophenone dimer (1-rac).

Nonlinear electrical conduction and broad band noise in the charge-ordered rare earth manganate Nd0.5Ca0.5MnO3

Measurements of the dc transport properties and the low-frequency conductivity noise in films of charge-ordered Nd0.5Ca0.5MnO3 grown on Si substrate reveal the existence of a threshold field in the charge-ordered regime beyond which strong nonlinear conduction sets in along with a large broad band conductivity noise. Threshold-dependent conduction disappears as T --> T-CO, the charge-ordering temperature. This observation suggests that the charge-ordered state gets depinned at the onset of the nonlinear conduction. (C) 1999 American Institute of Physics. [S0003-6951(99)05247-X].

Structural instability of the charge ordered compound Nd0.5Sr0.5MnO3 under a magnetic field

We report an anomalous magnetostriction behavior of the charge ordered compound Nd0.5Sr0.5MnO3. We have found that the applied magnetic field not only gives rise to a large negative magnetoresistance but also produces a huge positive magnetovolume effect. This unusual effect is explained considering that the applied magnetic field induces a structural transition at which the volume drastically increases. This effect is also seen in the anisotropic magnetostriction which shows clear anomalies at the field induced transition.

Synthesis and characterization of novel charge transfer complexes formed by N,N%-bis(ferrocenylmethylidene)-p-phenylenediamine and N-(ferrocenylmethylidene)aniline

N,N'-Bis(ferrocenylmethylidene)-p-phenylenediamine 1 and N-(ferrocenylmethylidene) aniline 2 are readily synthesized by Schiff base condensation of appropriate units. Iodine (I-2), 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), tetrachloro-1,4-benzoquinone (CA), tetracyanoethylene (TCNE) and 7,7,8,8-tetracyanoquinodimethane (TCNQ) form charge transfer complexes with 1 and 2. IR spectroscopy suggests an increase in the amount of charge transferred from the ferrocenyl ring to the oxidant in the order, I-2 < CA < TCNQ < TCNE approximate to DDQ. EPR spectra of the oxidized binuclear complexes are indicative of localized species containing iron- and carbon-centered radicals. The Mossbauer spectrum of the iodine oxidized complex of 1 reveals the presence of both Fe(III) and Fe(II) centers. Variable temperature magnetic and Mossbauer studies show that the ratio of Fe(III)/Fe(II) centers varies as a function of temperature. The larger Fe(II)/Fe(III) ratio at lower temperatures is best explained by a retro charge transfer from the iodide to the iron(III) metal center. There is negligible solvent effect on the formation of the iodine oxidized charge transfer complex of 1. (C) 1999 Elsevier Science S.A. All rights reserved.