Ab initio studies of solvent effect on conformational equilibria and vibrational spectra of dipropionamide

Systematic ab initio molecular orbital studies of the conformational equilibria and vibrational spectra of dipropionamide using the basis sets 6-31g(d) and 6-31++G(d,p) have been carried out. The vibrational spectra of dipropionamide have been satisfactorily interpreted taking into account the agreement between the calculated frequencies, infrared and Raman band intensities and the shifts in the spectra of deuterated molecules with those observed. The previous assignments of most of the vibrational bands are well confirmed, a few bands need reassignment, however. The solvent effects were investigated by self-consistent reaction field theory using dipole and self-consistent isodensity polarized continuum model methods. The introduction of a dielectric medium has only a marginal effect on the conformational equilibria and vibrational spectra. However, the calculated changes in geometry and vibrational spectra on going from the gas phase to the solution phase are in accord with the increasing weight of the dipolar resonance structure in polar solvents. (C) 2002 Elsevier Science B.V. All rights reserved.

Insulator-metal transition and magnetoresistance of La0.5Ca0.5MnOy induced by tuning the oxygen content

The oxygen content of La0.5Ca0.5MnOy was tuned by annealing the samples at high temperatures in flowing nitrogen with graphite powder nearby. The reduction of oxygen content has dramatic effect on the electrical transport and magnetic properties. The samples with y=2.983, 2.83, and 2.803 show an insulator-metal transition, and an unusual temperature and magnetic-field dependence of the magnetoresistance. The paramagnetic-ferromagnetic transition also shifts to lower temperatures and the antiferromagnetic transition at lower temperature is suppressed. The results are discussed in terms of the effect of oxygen vacancies on the various properties of La0.5Ca0.5MnOy. (C) 2002 American Institute of Physics.

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.

On the Magnetic Ground State of La(0.85)Sr(0.15)CoO(3) Single Crystals

We present an extensive study on magnetic and transport properties of La(0.85)Sr(0.15)CoO(3) single crystals grown by a float zone method to address the issue of phase separation versus spin-glass (SG) behavior. The dc magnetization study reveals a kink in field-cooled magnetization, and the peak in the zero-field-cooling curve shifts to lower temperature at modest dc fields, indicating the SG magnetic phase. The ac susceptibility study exhibits a considerable frequency-dependent peak shift (similar to 4 K) and a time-dependent memory effect below the freezing temperature. In addition, the characteristic time scale tau(0) estimated from the frequency-dependent ac susceptibility measurement is found to be similar to 10(-13) s, which matches well with typical values observed in canonical SG systems. The transport relaxation study evidently demonstrates the time-dependent glassy phenomena. In essence, all our experimental results corroborate the existence of SG behavior in La(0.85)Sr(0.15)CoO(3) single crystals.

An improved Monte Carlo scheme for simulation of synthesis of nanoparticles in reverse micelles

An improved Monte Carlo technique is presented in this work to simulate nanoparticle formation through a micellar route. The technique builds on the simulation technique proposed by Bandyopadhyaya et al. (Langmuir 2000, 16, 7139) which is general and rigorous but at the same time very computation intensive, so much so that nanoparticle formation in low occupancy systems cannot be simulated in reasonable time. In view of this, several strategies, rationalized by simple mathematical analyses, are proposed to accelerate Monte Carlo simulations. These are elimination of infructuous events, removal of excess reactant postreaction, and use of smaller micelle population a large number of times. Infructuous events include collision of an empty micelle with another empty one or with another one containing only one molecule or only a solid particle. These strategies are incorporated in a new simulation technique which divides the entire micelle population in four classes and shifts micelles from one class to other as the simulation proceeds. The simulation results, throughly tested using chi-square and other tests, show that the predictions of the improved technique remain unchanged, but with more than an order of magnitude decrease in computational effort for some of the simulations reported in the literature. A post priori validation scheme for the correctness of the simulation results has been utilized to propose a new simulation strategy to arrive at converged simulation results with near minimum computational effort.

Transmission electron microscopy study of domain structures in ferroelectric SrBi2Nb2O9 ceramics

A transmission electron microscopy study has been carried out on the domain structures of SrBi2Nb2O9 (SBN) ferroelectric ceramics which belong to the Aurivillius family of bismuth layered perovskite oxides. SBN is a potential candidate for Ferroelectric Random access memory (FeRAM) applications. The 90° ferroelectric domains and antiphase boundaries (APBs) were identified with dark field imaging techniques using different superlattice reflections which arise as a consequence of octahedral rotations and cationic shifts. The 90° domain walls are irregular in shape without any faceting. The antiphase boundaries are less dense compared to that of SrBi2Ta2O9(SBT). The electron microscopy observations are correlated with the polarization fatigue nature of the ceramic where the domain structures possibly play a key role in the fatigue- free behavior of the Aurivillius family of ferroelectric oxides.

Effect of Post-Metallization Hydrogen Annealing on C-V Characteristic of Zirconia Grown Using Atomic Layer Deposition

Substantial amount of fixed charge present in most of the alternative gate dielectrics gives rise to large shifts in the flat-band voltage (VFB) and charge trapping and de-trapping causes hysterectic changes on voltage cycling. Both phenomena affect stable and reliable transistor operation. In this paper we have studied for the first time the effect of post-metallization hydrogen annealing on the C-V curve of MOS capacitors employing zirconia, one of the most promising gate dielectric. Samples were annealed in hydrogen ambient for up to 30 minutes at different temperatures ranging from room temperature to 400°C. C-V measurements were done after annealing at each temperature and the hysteresis width was calculated from the C-V curves. A minimum hysteresis width of ∼35 mV was observed on annealing the sample at 200°C confirming the excellent suitability of this dielectric

Structural characterization of DC magnetron-sputtered TiO2 thin films using XRD and Raman scattering studies

Titanium dioxide films have been deposited using DC magnetron sputtering technique onto well-cleaned p-silicon substrates at an oxygen partial pressure of 7 x 10(-5) mbar and at a sputtering pressure (Ar + O-2) Of I X 10(-3) mbar. The deposited films were calcinated at 673 and 773 K. The composition of the films as analyzed using Auger electron spectroscopy reveals the stoichiometry with an 0 and Ti ratio 2.08. The influence of post-deposition annealing at 673 and 773 K on the structural properties of the titanium dioxide thin films have been studied using XRD and Raman scattering. The structure of the films deposited at the ambient was found to be amorphous and the films annealed at temperature 673 K and above were crystalline with anatase structure. The lattice constants, grain size, microstrain and the dislocation density of the film are calculated and correlated with annealing temperature. The Raman scattering study was performed on the as-deposited and annealed samples and the existence of Raman active modes A(1g), B-1g and E-g corresponding to the Raman shifts are studied and reported. The improvement of crystallinity of the TiO2 films was also studied using Raman scattering studies. (C) 2003 Elsevier Ltd. All rights reserved.

Correction for Bias in Downscaling GCM Simulations for Hydrologic Impact Assessment

In a statistical downscaling model, it is important to remove the bias of General Circulations Model (GCM) outputs resulting from various assumptions about the geophysical processes. One conventional method for correcting such bias is standardisation, which is used prior to statistical downscaling to reduce systematic bias in the mean and variances of GCM predictors relative to the observations or National Centre for Environmental Prediction/ National Centre for Atmospheric Research (NCEP/NCAR) reanalysis data. A major drawback of standardisation is that it may reduce the bias in the mean and variance of the predictor variable but it is much harder to accommodate the bias in large-scale patterns of atmospheric circulation in GCMs (e.g. shifts in the dominant storm track relative to observed data) or unrealistic inter-variable relationships. While predicting hydrologic scenarios, such uncorrected bias should be taken care of; otherwise it will propagate in the computations for subsequent years. A statistical method based on equi-probability transformation is applied in this study after downscaling, to remove the bias from the predicted hydrologic variable relative to the observed hydrologic variable for a baseline period. The model is applied in prediction of monsoon stream flow of Mahanadi River in India, from GCM generated large scale climatological data.

Groundwater Management in India:Physical, Institutional and Policy Alternatives

Groundwater constitutes a vital natural resource for sustaining India’s agricultural economy and meeting the country’s social, ecological and environmental goals. It is a unique resource, widely available, providing security against droughts and yet it is closely linked to surface-water resources and the hydrological cycle. Its availability depends on geo-hydrological conditions and characteristics of aquifers, from deep to alluvium, sediment crystalline rocks to basalt formations; and agro-climate from humid to subhumid and semi-arid to arid. Its reliable supply, uniform quality and temperature, relative turbidity, pollution-safe, minimal evaporation losses, and low cost of development are attributes making groundwater more attractive compared to other resources. It plays a key role in the provision of safe drinking water to rural populations. For example, already almost 80% of domestic water use in rural areas in India is groundwater-supplied, and much of it is being supplied to farms, villages and small towns. Inadequate control of the use of groundwater, indiscriminate application of agrochemicals and unrestrained pollution of the rural environment by other human activities make groundwater usage unsustainable, necessitating proper management in the face of the twin demand for water of good quality for domestic supply and adequate supply for irrigation, ensuring equity, efficiency and sustainability of the resource. Groundwater irrigation has overtaken surface irrigation in the early 1980s, supported by well energization. It is estimated that there are about 24 million energised wells and tube wells now and it is driven by demand rather than availability, evident through the greater occurrence of wells in districts with high population densities. Apart from aquifer characteristics, land fragmentation and landholding size are the factors that decide the density of wells. The ‘rise and fall’ of local economies dependent on groundwater can be summarized as: the green revolution of 1980s, groundwaterbased agrarian boom, early symptoms of groundwater overdraft, and decline of the groundwater socio-ecology. The social characteristics and policy interventions typical of each stage provide a fascinating insight into the human-resource dynamics. This book is a compilation of nine research papers discussing various aspects of groundwater management. It attempts to integrate knowledge about the physical system, the socio-economic system, the institutional set-up and the policy environment to come out with a more realistic analysis of the situation with regard to the nature, characteristics and intensity of resource use, the size of the economy the use generates, and the negative socioeconomic consequences. Complex variables addressed in this regard focusing on northern Gujarat are the stock of groundwater available in the region, its hydrodynamics, its net outflows against inflows, the economics of its intensive use (particularly irrigation in semi-arid and arid regions), its criticality in the regional hydroecological regime, ethical aspects and social aspects of its use. The first chapter by Dinesh Kumar and Singh, dwells on complex groundwater socio-ecology of India, while emphasizing the need for policy measures to address indiscriminate over-exploitation of dwindling resources. The chapter also explores the nature of groundwater economy and the role of electricity prices on it. The next chapter on groundwater issue in north Gujarat provides a description of groundwater resource characteristics followed by a detailed analysis of the groundwater depletion and quality deterioration problems in the region and their undesirable consequences on the economy, ecosystem health and the society. Considering water-buyers and wellowning farmers individually, a methodology for economic valuation of groundwater in regions where its primary usage is in agriculture, and as assessment of the groundwater economy based on case studies from north Gujarat is presented in the fourth chapter. The next chapter focuses on the extent of dependency of milk production on groundwater, which includes the water embedded in green and dry fodder and animal feed. The study made a realistic estimate of irrigation water productivity in terms of the physics and economics of milk production. The sixth chapter analyses the extent of reduction in water usage, increase in yield and overall increase in physical productivity of alfalfa with the use of the drip irrigation system. The chapter also provides a detailed synthesis of the costs and benefits associated with the use of drip irrigation systems. A linear programmingbased optimization model with the objective to minimize groundwater use taking into account the interaction between two distinct components – farming and dairying under the constraints of food security and income stability for different scenarios, including shift in cropping pattern, introduction of water-efficient crops, water- saving technologies in addition to the ‘business as usual’ scenario is presented in the seventh chapter. The results show that sustaining dairy production in the region with reduced groundwater draft requires crop shifts and adoption of water-saving technologies. The eighth chapter provides evidences to prove that the presence of adequate economic incentive would encourage farmers to adopt water-saving irrigation devices, based on the findings of market research with reference to the level of awareness among farmers of technologies and the factors that decide the adoption of water-saving technologies. However, now the marginal cost of using electricity for agricultural pumping is almost zero. The economic incentives are strong and visible only when the farmers are either water-buyers or have to manage irrigation with limited water from tube-well partnerships. The ninth chapter explores the socio-economic viability of increasing the power tariff and inducing groundwater rationing as a tool for managing energy and groundwater demand, considering the current estimate of the country’s annual economic loss of Rs 320 billion towards electricity subsidy in the farm sector. The tenth chapter suggests private tradable property rights and development of water markets as the institutional tool for achieving equity, efficiency and sustainability of groundwater use. It identifies the externalities for local groundwater management and emphasizes the need for managing groundwater by local user groups, supported by a thorough analysis of groundwater socio-ecology in India. An institutional framework for managing the resource based on participatory approach that is capable of internalizing the externalities, comprising implementation of institutional and technical alternatives for resource management is also presented. Major findings of the analyses and key arguments in each chapter are summarized in the concluding chapter. Case studies of the social and economic benefits of groundwater use, where that use could be described as unsustainable, are interesting. The benefits of groundwater use are outlined and described with examples of social and economic impacts of groundwater and the negative aspects of groundwater development with the compilation of environmental problems based on up-to-date research results. This publication with a well-edited compilation of case studies is informative and constitutes a useful publication for students and professionals.

Quantum Algorithms with Fixed Points: The Case of Database Search

The standard quantum search algorithm lacks a feature, enjoyed by many classical algorithms, of having a fixed-point, i.e. a monotonic convergence towards the solution. Here we present two variations of the quantum search algorithm, which get around this limitation. The first replaces selective inversions in the algorithm by selective phase shifts of $\frac{\pi}{3}$. The second controls the selective inversion operations using two ancilla qubits, and irreversible measurement operations on the ancilla qubits drive the starting state towards the target state. Using $q$ oracle queries, these variations reduce the probability of finding a non-target state from $\epsilon$ to $\epsilon^{2q+1}$, which is asymptotically optimal. Similar ideas can lead to robust quantum algorithms, and provide conceptually new schemes for error correction.

Colorimetric Probes Based on Anthraimidazolediones for Selective Sensing of Fluoride and Cyanide Ion via Intramolecular Charge Transfer

Probes based on anthra[1,2-d]imidazole-6,11-dione were designed and synthesized for selective ion sensing. Each probe acted as strong colorimetric sensors for fluoride and cyanide ions and exhibited intramolecular charge transfer (ICT) band, which showed significant red-shifts after addition of either the F(-) or CN(-) ion. One of the probes (2) showed selective colorimetric sensing for both cyanide and fluoride ions. In organic medium, 2 showed selective color change with fluoride and cyanide, whereas in aqueous organic medium it showed a ratiometric response selectively for cyanide ion.

Synthesis, Characterization, and Electronic Structure of New Type of Heterometallic Boride Clusters

The reaction of [Cp*TaCl(4)], 1 (Cp* = eta(5)-C(5)Me(5)), with [LiBH(4)center dot THF] at -78 degrees C, followed by thermolysis in the presence of excess [BH(3)center dot THF], results in the formation of the oxatantalaborane cluster [(Cp*Ta)(2)B(4)H(10)O], 2 in moderate yield. Compound 2 is a notable example of an oxatantalaborane cluster where oxygen is contiguously bound to both the metal and boron. Upon availability of 2, a room temperature reaction was performed with [Fe(2)(CO)(9)], which led to the isolation of [(Cp*Ta)(2)B(2)H(4)O{H(2)Fe(2)(CO)(6)BH} ] 3. Compound 3 is an unusual heterometallic boride cluster in which the [Ta(2)Fe(2)] atoms define a butterfly framework with one boron atom lying in a semi-interstitial position. Likewise, the diselenamolybdaborane, [(Cp*Mo)(2)B(4)H(4)Se(2)], 4 was treated with an excess of [Fe(2)(CO)(9)] to afford the heterometallic boride cluster [(Cp*MoSe)(2)Fe(6)(CO)(13)B(2)(BH)(2)], 5. The cluster core of 5 consists of a cubane [Mo(2)Se(2)Fe(2)B(2)] and a tricapped trigonal prism [Fe(6)B(3)] fused together with four atoms held in common between the two subclusters. In the tricapped trigonal prism subunit, one of the boron atoms is completely encapsulated and bonded to six iron and two boron atoms. Compounds 2, 3, and 5 have been characterized by mass spectrometry, IR, (1)H, (11)B, (13)C NMR spectroscopy, and the geometric structures were unequivocally established by crystallographic analysis. The density functional theory calculations yielded geometries that are in close agreement with the observed structures. Furthermore, the calculated (11)B NMR chemical shifts also support the structural characterization of the compounds. Natural bond order analysis and Wiberg bond indices are used to gain insight into the bonding patterns of the observed geometries of 2, 3, and 5.

Kinetics and chemical analysis of photoinduced interdiffusion in nanolayered Se/As2S3 films

We have studied the kinetics of photoinduced effects in nanolayered Se/As2S3 film by in situ optical absorption measurements, which reveal that photodarkening in these films is followed by photoinduced diffusion. An increase in disorder during photodarkening and its subsequent decrease during photoinduced diffusion were also observed. The observation of photodarkening of Se at room temperature when confined between As2S3 layers suggests that the glass transition temperature of Se shifts to higher energy. The analysis shows that the atoms which take part in photodarkening play a vital role in photoinduced diffusion. The x-ray photoelectron spectroscopy measurements show the atomic movements during photoinduced diffusion. It also shows that some of the As–S bonds are converted into As–Se bonds. Since it is energetically difficult to break an As–S bond to form an As–Se bond, we assume that the new bond formations are taking place by the bond rearrangement mechanism.

Evidence for decoupled two-dimensional vortex behavior of YBa2Cu3O7-δ in La0.7Sr0.3MnO3/YBa2Cu3O7-δ/La0.7Sr0.3MnO3 trilayer

We investigate the vortex behavior of YBa2Cu3O7−δ thin films sandwiched between two ferromagnetic layers (La0.7Sr0.3MnO3/YBa2Cu3O7−δ/La0.7Sr0.3MnO3). The magnetization study on La0.7Sr0.3MnO3/YBa2Cu3O7−δ/La0.7Sr0.3MnO3 trilayers conspicuously shows the presence of both ferromagnetic and diamagnetic phases. The magnetotransport study on the trilayers reveals a significant reduction in the activation energy (U) for the vortex motion in YBa2Cu3O7−δ. Besides, the “U” exhibits a logarithmic dependence on the applied magnetic field which directly indicates the existence of decoupled two-dimensional (2D) pancake vortices present in the CuO2 layers. The evidence of 2D decoupled vortex behavior in La0.7Sr0.3MnO3/YBa2Cu3O7−δ/La0.7Sr0.3MnO3 is believed to arise from (a) the weakening of superconducting coherence length along the c-axis and (b) enhanced intraplane vortex–vortex interaction due to the presence of ferromagnetic layers.