1, 2-Bis (diphenylphosphino) etane bridged dinuclear copper (I) complexes: Investigations of solid state and solution structures by CP/MAS31P NMR spectroscopy, X-ray crystallography, IR spectroscopy and solution 31P NMR and 63Cu NMR spectroscopy

Three different complexes of copper (I) with bridging 1, 2-bis(diphenylphosphino)ethane (dppe), namely [Cu2 (mu-dppe) (CH3CN)6] (ClO4)2 (1), [Cu2 (mu-dppe)2 (CH3 CN)2] (ClO4)2 (2), and [Cu2 (mu-dppe) (dppe)2 (CH3CN)2] (ClO4)2 (3) have been prepared. The structure of [Cu2 (mu-dppe) (dPPe)2 (CH3CH)2] (ClO4)2 has been determined by X-ray crystallography. It crystallizes in the space group PT with a=12.984(6) angstrom, b=13.180(6) angstrom, c=14.001(3) angstrom, alpha=105.23(3), beta=105.60(2), gamma=112.53 (4), V=1944 (3) angstrom3, and Z=1. The structure was refined by least-squares method with R=0.0365; R(w)=0.0451 for 6321 reflections with F0 greater-than-or-equal-to 3 sigma (F0). The CP/MAS P-31 and IR spectra of the complexes have been analysed in the light of available crystallographic data. IR spectroscopy is particularly helpful in identifying the presence of chelating dppe. P-31 chemical shifts observed in solid state are very different from those observed in solution, and change significantly with slight changes in structure. In solution, complex 1 remains undissociated but complexes 2 and 3 undergo extensive dissociation. With a combination of room temperature H-1, Cu-63, and variable temperature P-31 NMR spectra, it is possible to understand the various processes occurring in solution.

Four decades of research in solid state chemistry

Solid state chemistry was in its infancy when the author got interested in the subject. In this article, the author outlines the manner in which the subject has grown over the last four decades, citing representative examples from his own contributions to the different facets of the subject. The various aspects covered include synthesis, structure, defects, phase transitions, transition metal oxides, catalysts, superconductors, metal clusters and fullerenes. In an effort to demonstrate the breadth and vitality of the subject, the author shares his own experiences and aspirations and gives expression to the agony and ecstacy in carrying out experimental research in such a frontier area in India.

Temperature-dependent chirped coherent phonon dynamics in Bi2Te3 using high-intensity femtosecond laser pulses

Degenerate pump-probe reflectivity experiments have been performed on a single crystal of bismuth telluride (Bi2Te3) as a function of sample temperature (3 K to 296 K) and pump intensity using similar to 50 femtosecond laser pulses with central photon energy of 1.57 eV. The time-resolved reflectivity data show two coherently generated totally symmetric A(1g) modes at 1.85 THz and 3.6 THz at 296 K which blue-shift to 1.9 THz and 4.02 THz, respectively, at 3 K. At high photoexcited carrier density of similar to 1.7 x 10(21) cm(-3), the phonon mode at 4.02 THz is two orders of magnitude higher positively chirped (i.e the phonon time period decreases with increasing delay time between the pump and the probe pulses) than the lower-frequency mode at 1.9 THz. The chirp parameter, beta is shown to be inversely varying with temperature. The time evolution of these modes is studied using continuous-wavelet transform of the time-resolved reflectivity data. Copyright (C) EPLA, 2010

Coherent rainfall zones of the Indian region

We have delineated rainfall zones for the Indian region that are coherent with respect to the variations of the summer monsoon rainfall. Within each zone, the time series of the summer monsoon rainfall at every pair of stations are significantly positively correlated, and the mean interseries correlation for each zone is high. The interseries correlation data set is analysed in order to delineate the rainfall zones, using an objective method specifically developed for the purpose. Each of the zonal averages are shown to be representative of the zone as a whole. We suggest that this regionalization is appropriate for study of the variation of the summer monsoon rainfall over the Indian region on interannual and larger scales.

Denumerable state stochastic games with limiting average payoff

We study stochastic games with countable state space, compact action spaces, and limiting average payoff. ForN-person games, the existence of an equilibrium in stationary strategies is established under a certain Liapunov stability condition. For two-person zero-sum games, the existence of a value and optimal strategies for both players are established under the same stability condition.

Influence of state of stress on the processing map for hot working of stainless steel type AISI 304L: compression vs. torsion

Processing maps for hot working of stainless steel of type AISI 304L have been developed on the basis of the flow stress data generated by compression and torsion in the temperature range 600–1200 °C and strain rate range 0.1–100 s−1. The efficiency of power dissipation given by 2m/(m+1) where m is the strain rate sensitivity is plotted as a function of temperature and strain rate to obtain a processing map, which is interpreted on the basis of the Dynamic Materials Model. The maps obtained by compression as well as torsion exhibited a domain of dynamic recrystallization with its peak efficiency occurring at 1200 °C and 0.1 s−1. These are the optimum hot-working parameters which may be obtained by either of the test techniques. The peak efficiency for the dynamic recrystallization is apparently higher (64%) than that obtained in constant-true-strain-rate compression (41%) and the difference in explained on the basis of strain rate variations occurring across the section of solid torsion bar. A region of flow instability has occurred at lower temperatures (below 1000 °C) and higher strain rates (above 1 s−1) and is wider in torsion than in compression. To achieve complete microstructure control in a component, the state of stress will have to be considered.

Interaction of C60 and C70 with aromatic amines in the ground and excited states. Evindence for fullerene—benzene interaction in the ground state

While C60 interacts with aromatic amines such as dimethylaniline in the ground state, C70 does not. Fluorescence spectroscopic studies, including lifetime measurements, show the formation of exciplexes of both C60 and C70 with aromatic amines in nonaromatic solvents such as methylcyclohexane. Exciplexes are however not formed in benzene solvent, due to π—π interaction between benzene and the fullerene. Based on spectroscopic absorption measurements, it is shown that both C60 and C70 do indeed interact with benzene in the ground state.

Is tetramethyleneethane a ground state triplet?

We have examined a number of possible ways by which tetramethyleneethane (TME) can be a ground state triplet, as claimed by experimental studies, in violation of Ovchinnikov’s theorem for alternant hydrocarbons of equal bond lengths. Model exact π calculations of the low-lying states of TME, 3,4-dimethylenefuran and 3,4-dimethylenepyrrole were carried out using a diagrammatic valence bond approach. The calculations failed to yield a triplet ground state even after (a) tuning of electron correlation, (b) breaking alternancy symmetry, and (c) allowing for geometric distortions. In contrast to earlier studies of fine structure constants in other conjugated systems, the computedD andE values of all the low-lying triplet states of TME for various geometries are at least an order of magnitude different from the experimentally reported values. Incorporation of σ-π mixing by means of UHF MNDO calculations is found to favour a singlet ground state even further. A reinterpretation of the experimental results of TME is therefore suggested to resolve the conflict.

Current State of Domestic Concealed Wiring Practices in Bangalore, India

In a modernising world, building and construction trends in recent urban centres such as Bangalore, set precedence for developments in other urban centres of the country. Under such conditions, evaluating the current state of building practices could prove useful for identifying the likely nature of nationwide building trends. This paper comprises a study to evaluate the current state of domestic concealed wiring practices in the context of a modern urban centre area in India. Presently, concealed wiring is the predominant wiring method adopted for residences, both bungalows and apartments. A modern residential block in the city of Bangalore (India) was chosen as the study area. The study included extensive interaction and surveys amongst residents, professionals (architects and engineers) and site personnel (contractors and electricians). In addition, the study also included site verification on the state of wiring practices in the residential block. The study indicates that while aesthetics was the prime reason that dictated the choice of concealed wiring, its effectiveness as an appropriate and safe wiring method is severely compromised. Details of the study, results and recommendations are presented in this paper.

Meridional propagation of large-scale monsoon convective zones

Observational studies indicate that the convective activity of the monsoon systems undergo intraseasonal variations with multi-week time scales. The zone of maximum monsoon convection exhibits substantial transient behavior with successive propagating from the North Indian Ocean to the heated continent. Over South Asia the zone achieves its maximum intensity. These propagations may extend over 3000 km in latitude and perhaps twice the distance in longitude and remain as coherent entities for periods greater than 2-3 weeks. Attempts to explain this phenomena using simple ocean-atmosphere models of the monsoon system had concluded that the interactive ground hydrology so modifies the total heating of the atmosphere that a steady state solution is not possible, thus promoting lateral propagation. That is, the ground hydrology forces the total heating of the atmosphere and the vertical velocity to be slightly out of phase, causing a migration of the convection towards the region of maximum heating. Whereas the lateral scale of the variations produced by the Webster (1983) model were essentially correct, they occurred at twice the frequency of the observed events and were formed near the coastal margin, rather than over the ocean. Webster's (1983) model used to pose the theories was deficient in a number of aspects. Particularly, both the ground moisture content and the thermal inertia of the model were severely underestimated. At the same time, the sea surface temperatures produced by the model between the equator and the model's land-sea boundary were far too cool. Both the atmosphere and the ocean model were modified to include a better hydrological cycle and ocean structure. The convective events produced by the modified model possessed the observed frequency and were generated well south of the coastline. The improved simulation of monsoon variability allowed the hydrological cycle feedback to be generalized. It was found that monsoon variability was constrained to lie within the bounds of a positive gradient of a convective intensity potential (I). The function depends primarily on the surface temperature, the availability of moisture and the stability of the lower atmosphere which varies very slowly on the time scale of months. The oscillations of the monsoon perturb the mean convective intensity potential causing local enhancements of the gradient. These perturbations are caused by the hydrological feedbacks, discussed above, or by the modification of the air-sea fluxes caused by variations of the low level wind during convective events. The final result is the slow northward propagation of convection within an even slower convective regime. The ECMWF analyses show very similar behavior of the convective intensity potential. Although it is considered premature to use the model to conduct simulations of the African monsoon system, the ECMWF analysis indicates similar behavior in the convective intensity potential suggesting, at least, that the same processes control the low frequency structure of the African monsoon. The implications of the hypotheses on numerical weather prediction of monsoon phenomenon are discussed.

Aspects of coherent states of nonlinear algebras

Various aspects of coherent states of nonlinear su(2) and su(1,1) algebras are studied. It is shown that the nonlinear su(1,1) Barut-Girardello and Perelomov coherent states are related by a Laplace transform. We then concentrate on the derivation and analysis of the statistical and geometrical properties of these states. The Berry's phase for the nonlinear coherent states is also derived. (C) 2010 American Institute of Physics. doi:10.1063/1.3514118]

Prediction of the Indian summer monsoon rainfall using a state-of-the-art coupled ocean-atmosphere model

A state-of-the-art model of the coupled ocean-atmosphere system, the climate forecast system (CFS), from the National Centres for Environmental Prediction (NCEP), USA, has been ported onto the PARAM Padma parallel computing system at the Centre for Development of Advanced Computing (CDAC), Bangalore and retrospective predictions for the summer monsoon (June-September) season of 2009 have been generated, using five initial conditions for the atmosphere and one initial condition for the ocean for May 2009. Whereas a large deficit in the Indian summer monsoon rainfall (ISMR; June-September) was experienced over the Indian region (with the all-India rainfall deficit by 22% of the average), the ensemble average prediction was for above-average rainfall during the summer monsoon. The retrospective predictions of ISMR with CFS from NCEP for 1981-2008 have been analysed. The retrospective predictions from NCEP for the summer monsoon of 1994 and that from CDAC for 2009 have been compared with the simulations for each of the seasons with the stand-alone atmospheric component of the model, the global forecast system (GFS), and observations. It has been shown that the simulation with GFS for 2009 showed deficit rainfall as observed. The large error in the prediction for the monsoon of 2009 can be attributed to a positive Indian Ocean Dipole event seen in the prediction from July onwards, which was not present in the observations. This suggests that the error could be reduced with improvement of the ocean model over the equatorial Indian Ocean.