Spin state and exchange in the quasi-one-dimensional antiferromagnet KFeS2

We report the optical spectra and single crystal magnetic susceptibility of the one-dimensional antiferromagnet KFeS2. Measurements have been carried out to ascertain the spin state of Fe3+ and the nature of the magnetic interactions in this compound. The optical spectra and magnetic susceptibility could be consistently interpreted using a S = 1/2 spin ground state for the Fe3+ ion. The features in the optical spectra have been assigned to transitions within the d-electron manifold of the Fe3+ ion, and analysed in the strong field limit of the ligand field theory. The high temperature isotropic magnetic susceptibility is typical of a low-dimensional system and exhibits a broad maximum at similar to 565 K. The susceptibility shows a well defined transition to a three dimensionally ordered antiferromagnetic state at T-N = 250 K. The intra and interchain exchange constants, J and J', have been evaluated from the experimental susceptibilities using the relationship between these quantities, and chi(max), T-max, and T-N for a spin 1/2 one-dimensional chain. The values are J = -440.71 K, and J' = 53.94 K. Using these values of J and J', the susceptibility of a spin 1/2 Heisenberg chain was calculated. A non-interacting spin wave model was used below T-N. The susceptibility in the paramagnetic region was calculated from the theoretical curves for an infinite S = 1/2 chain. The calculated susceptibility compares well with the experimental data of KFeS2. Further support for a one-dimensional spin 1/2 model comes from the fact that the calculated perpendicular susceptibility at 0K (2.75 x 10(-4) emu/mol) evaluated considering the zero point reduction in magnetization from spin wave theory is close to the projected value (2.7 x 10(-4) emu/mol) obtained from the experimental data.

Steady state three-dimensional mathematical model for cupola

A three-dimensional mathematical model has been developed to simulate the gas flow, composition, and temperature profiles inside a cupola. Comparison of the model with the reported experimental data shows the presence of a zone with low combustion rate at the tuyere level. For a 24 in (610 mm) cupola with four rows of tuyeres, the combustion zones from each tuyere overlap each other, forming an overall combustion zone of cylindrical shape of height similar to 0.2 m. Using the model, it is found that the spout temperature initially increases with increasing blast velocity and attains a maximum. Further increase in blast velocity does not change the spout temperature. This suggests that smaller size tuyeres and higher permeability of the bed can give superior cupola performance. (C) 1997 The Institute of Materials.

Stereospecific solid-state NaBH4-promoted reduction of 1-methylpentacyclo[5.4.0.0(2,6).0(3,10).0(5,9)]undecane-8,11-dione

NaBH4 reduction of a cage dione proceeds in a stereospecific fashion to give the endo,endo-diol. This reactivity is related to the crystal structure.

Structural and conformational study of peptides containing glycine and alanine residues by C-13 CPMAS NMR spectroscopy in solid state

The results of the structural and conformational studies carried out using C-13 CPMAS NMR technique on several glycine and alanine containing peptides in the solid state are reported. The study demonstrates the effects of variations in C-13 chemical shifts due to conformation and hydrogen bonding. The possibility of applying this technique to obtain insight into the conformational characteristics of peptides of unknown structures is discussed.

The physics and technology of gallium antimonide: An emerging optoelectronic material

Recent advances in nonsilica fiber technology have prompted the development of suitable materials for devices operating beyond 1.55 mu m. The III-V ternaries and quaternaries (AlGaIn)(AsSb) lattice matched to GaSb seem to be the obvious choice and have turned out to be promising candidates for high speed electronic and long wavelength photonic devices. Consequently, there has been tremendous upthrust in research activities of GaSb-based systems. As a matter of fact, this compound has proved to be an interesting material for both basic and applied research. At present, GaSb technology is in its infancy and considerable research has to be carried out before it can be employed for large scale device fabrication. This article presents an up to date comprehensive account of research carried out hitherto. It explores in detail the material aspects of GaSb starting from crystal growth in bulk and epitaxial form, post growth material processing to device feasibility. An overview of the lattice, electronic, transport, optical and device related properties is presented. Some of the current areas of research and development have been critically reviewed and their significance for both understanding the basic physics as well as for device applications are addressed. These include the role of defects and impurities on the structural, optical and electrical properties of the material, various techniques employed for surface and bulk defect passivation and their effect on the device characteristics, development of novel device structures, etc. Several avenues where further work is required in order to upgrade this III-V compound for optoelectronic devices are listed. It is concluded that the present day knowledge in this material system is sufficient to understand the basic properties and what should be more vigorously pursued is their implementation for device fabrication. (C) 1997 American Institute of Physics.

Time-resolved resonance Raman spectroscopic studies on the triplet excited state of fluoranil

Perfluoro substituted organic compounds have attracted attention owing to their unique structure and reactivity induced by the perfluoro effect. Fluoranil, a perfluoro derivative of p-benzoquinone, is the subject of this paper. Although the perfluoro effect in the ground state seems to have been well understood there is no information available about such effects on the excited state. Here, the time-resolved resonance Raman spectra of the triplet excited state of fluoranil are reported along with the Raman excitation profiles (REPs) of the various vibrational modes. The vibrational spectral analyses have been carried out by analogy with the fluoranil ground state, triplet benzoquinone, and triplet chloranil vibrational spectral assignments. Also, the assignments are further supported by the calculated frequencies using ab initio theoretical methods. It is observed that for fluoranil in the triplet excited state, due to the perfluoro effect, the structure is considerably less distorted than benzoquinone and also the electron delocalization in the pi* antibonding orbital is less than that of triplet excited state of benzoquinone.

Volume modelling for emerging manufacturing technologies

The next generation manufacturing technologies will draw on new developments in geometric modelling. Based on a comprehensive analysis of the desiderata of next generation geometric modellers, we present a critical review of the major modelling paradigms, namely, CSG, B-Rep, non-manifold, and voxel models. We present arguments to support the view that voxel-based modellers have attributes that make it the representation scheme of choice in meeting the emerging requirements of geometric modelling.

Modeling and control of unified power flow controller for transient stability

FACTS controllers are emerging as viable and economic solutions to the problems of large interconnected ne networks, which can endanger the system security. These devices are characterized by their fast response, absence of inertia, and minimum maintenance requirements. Thyristor controlled equipment like Thyristor Controlled Series Capacitor (TCSC), Static Var Compensator (SVC), Thyristor Controlled Phase angle Regulator (TCPR) etc. which involve passive elements result in devices of large sizes with substantial cost and significant labour for installation. An all solid-state device using GTOs leads to reduction in equipment size and has improved performance. The Unified Power Flow Controller (UPFC) is a versatile controller which can be used to control the active and reactive power in the Line independently. The concept of UPFC makes it possible to handle practically all power flow control and transmission line compensation problems, using solid-state controllers, which provide functional flexibility, generally not attainable by conventional thyristor controlled systems. In this paper, we present the development of a control scheme for the series injected voltage of the UPFC to damp the power oscillations and improve transient stability in a power system. (C) 1998 Elsevier Science Ltd. All rights reserved.

Stability of degenerate diffusions with state-dependent switching

This paper deals with the ergodic properties of hybrid systems modelled by diffusion processes with state-dependent switching. We investigate the sufficient conditions expressed in terms of the parameters of the underlying process which would ensure the existence of a unique invariant probability and stability in distribution of the flow. It turns out that the conditions would depend on certain averaging mechanisms over the states of the discrete component of the hybrid system. (C) 1999 Academic Press.

The steady state nuclear Overhauser effect revisited

The steady state of a two spin system coupled to an isotropic environment and to each other through a dipolar interaction and under irradiation by a monochromatic, circularly polarized radio frequency field is determined ab initio using thermodynamic arguments. This steady state is used to describe the well known nuclear Overhauser effect in liquids. The steady state is also derived from the Solomon-Bloch set of equations used to describe the driven spin. It is shown that in the limit of weak driving, the two solutions coincide. (C) 1999 American Institute of Physics. [S0021-9606(99)71210-9].

Difference in spin state and covalence between La1-xSrxCoO3 and La2-xSrxLi0.5Co0.5O4

We present a comparative study of the spin states and electronic properties of La1-xSrxCoO3 and La2-xSrxLi0.5Co0.5O4 using X-ray absorption near-edge structure spectroscopy at both the O-K and Co-L-2.3 thresholds. In the La2-xSrxLi0.5Co0.5O4 system the CoO6 octahedra are isolated, the holes induced by Sr doping are trapped in the isolated Co(IV)O-6 octahedra, and a low-spin state is found for the Co ions, which does not change upon Sr doping. In the La1-xSrxCoO3 system, the interconnected CoO6 octahedra, with a 180degrees Co-O-Co bond angle, give rise to a transition from low-spin to intermediate-spin state with a ferromagnetic alignment of the Co spins. The double-exchange, ferromagnetic coupling between Co ions mediated by the 180degrees bond angle is responsible for suppressing the low spin-state. We find that the branching ratio of spectral intensities at the L-2 and L-3 thresholds in the Co-L-2.3 X-ray absorption spectra is sensitive to the spin state of the Co ions allowing its direct spectroscopic determination. (C) 2002 Published by Elsevier Science B.V.

Electrochemical studies of polyaniline in a gel polymer electrolyte - High energy and high power characteristics of a solid-state redox supercapacitor

Studies on redox supercapacitors employing electronically conducting polymers are of great importance for hybrid power sources and pulse power applications. In the present study, polyaniline (PANI) has been potentiodynamically deposited on stainless steel substrate and characterized in a gel polymer electrolyte (GPE). Use of the GPE facilitates a voltage limit of the capacitor to 1 V, instead of 0.75 V in aqueous electrolytes. From charge-discharge studies of the solid-state PANI capacitors, a specific capacitance of 250 F g(-1) has been obtained at a specific power of 7.5 kW kg(-1) of PANI. The values of specific capacitance and specific power are considerably higher than those reported in the literature. High energy and high power characteristics of the PANI are presented. (C) 2002 The Electrochemical Society.

Excited state structure and dynamics of p-benzoquinone and bromanil from time-resolved resonance Raman spectra and simulation

p-Benzoquinone and its halogen substituted derivatives are known to have differing reactivities in the triplet excited state. While bromanil catalyzes the reduction of octaethylporphyrin most efficiently among the halogenated p-benzoquinones, the reaction does not take place in presence of the unsubstituted p-benzoquinone (T. Nakano and Y. Mori, Bull. Chem. Soc. Jpn., 67, 2627 (1994)). Understanding of such differences requires a detailed knowledge of the triplet state structures, normal mode compositions and excited state dynamics. In this paper, we apply a recently presented scheme (M. Puranik, S. Umapathy, J. G. Snijders, and J. Chandrasekhar, J. Chem, Phys., 115, 6106 (2001)) that combines parameters from experiment and computation in a wave packet dynamics simulation to the triplet states of p-benzoquinone and bromanil. The absorption and resonance Raman spectra of both the molecules have been simulated. The normal mode compositions and mode specific excited state displacements have been presented and compared. Time-dependent evolution of the absorption and Raman overlaps for all the observed modes has been discussed in detail. In p-benzoquinone, the initial dynamics is along the C=C stretching and C-H bending modes whereas in bromanil nearly equal displacements are observed along all the stretching coordinates.

A determination of the structure of the intramolecular charge transfer state of 4-dimethylaminobenzonitrile (DMABN) by time-resolved resonance Raman spectroscopy

Picosecond time-resolved resonance Raman spectra of the A (intramolecular charge transfer, ICT) state of DMABN, DMABN-d(6) and DMABN-N-15 have been obtained. The isotopic shifts identify the nu (s)(ph-N) mode as a band at 1281 cm(-1). The similar to 96 cm(-1) downshift of this mode from its ground state frequency rules out the electronic coupling PICT model and unequivocally supports the electronic decoupling TICT model. However, our results suggest some pyramidal character of the A state amino conformation.

Photochemical behaviour of 4-styrylcoumarin polymorphs in the crystalline state

Addition of a small amount of coumarin during crystallization produces new polymorphic modifications in 4-styrylcoumarin and 4-(3-fluorostyryl)coumarin, which are photolabile. Interestingly, upon irradiation polymorphic modification of 4-(3-fluorostyryl)coumarin produces a mirror-symmetric photodimer in contrast to the centrosymmetric photodimer obtained without addition of coumarin during crystallization.