Photodissociation dynamics of CH2ICl at 222, 236, 266, 280, and-304 nm

Dynamics of I*(P-2(1/2)) formation from CH2ICl dissociation has-been investigated at five different ultraviolet excitation wavelengths, e.g., 222, 236, 266, 280, and similar to304 nm. The quantum yield of I*((2)p(1/2)) production, phi*, has been measured by monitoring nascent I(P-2(3/2)) and I* concentrations using a resonance enhanced multiphoton ionization detection scheme. The measured quantum yield as a function of excitation energy follows the same trend as that of methyl iodide except at 236 run. The photodissociation dynamics of CH2ICl also involves three upper states similar to methyl iodide, and a qualitative correlation diagram has been constructed to account for the observed quantum yield. From the difference in behavior at 236 nm, it appears that the crossing region between the two excited states ((3)Q(0) and (1)Q(1)) is located near the exit valley away from the Franck Condon excitation region. The B- and C-band transitions do not participate in the dynamics, and the perturbation of the methyl iodide states due to Cl-I interaction is relatively weak at the photolysis wavelengths employed in this investigation.

Slow orientational dynamics of water molecules at a micellar surface

The dynamics of water molecules near an aqueous micellar interface is studied in an atomistic molecular dynamics simulation of cesium pentadecafluorooctanoate (CsPFO) in water. The dipolar orientational time correlation function (tcf) and the translational diffusion of the water molecules are investigated. Results show that both the reorientational and the translational motion of water molecules near the micelle are restricted. In particular, the orientational tcf exhibits a very slow component in the long time which is slower than its bulk value by 2 orders of magnitude. This slow decay seems to be related to the slow decay often observed in experiments. The origin of the slow decay is analyzed.

Study of translational and rotational mobility and orientational preference of ethane in one-dimensional channels

Structural and dynamical properties of ethane in one-dimensional channels of AlPO4-5 and carbon nanotube have been investigated at dilute concentration with the help of molecular dynamics simulation. Density distributions and orientational structure of ethane have been analyzed. Repulsive interactions seem to play an important role when ethane is located in the narrow part of the AlPO4-5 channel. In AlPO4-5, parallel orientation is predominant over perpendicular orientation except when ethane is located in the broader part of the channel. Unlike in the case of single-file diffusion, our results in carbon nanotube show that at dilute concentrations the mean squared displacement, mu(2)(t) approximate to t(alpha), alpha = 1.8. The autocorrelation function for the z-component of angular velocity of ethane in space-fixed frame of reference shows a pronounced negative correlation. This is attributed to the restriction in the movement of ethane along the x- and y- directions. It is seen that the ratio of reorientational correlation times does not follow the Debye model for confined ethane but it is closer to the predictions of the Debye model for bulk ethane.

Unimolecular HCl elimination from 1,2-dichloroethane: A single pulse shock tube and ab initio study

Thermal decomposition of 1,2-dichloroethane (1,2-DCE) has been studied in the temperature range of 10501175 K behind reflected shock waves in a single pulse shock tube. The unimolecular elimination of HCl is found to be the major channel through which 1,2-DCE decomposes under these conditions. The rate constant for the unimolecular elimination of HCl from 1,2-dichloroethane is found to be 10(13.98+/-0.80) exp(-57.8+/-2.0/RT) s(-1), where the activation energy is given in kcal mol(-1) and is very close to that value for CH3CH2Cl (EC). Ab initio (HF and MP2) and DFT calculations have been carried out to find the activation barrier and the structure of the transition state for this reaction channel from both EC and 1,2-DCE. The preexponential factors calculated at various levels of theory (BF/6-311++G**, MP2/6-311++G**, and B3LYP/6-311++G**) are (approximate to10(15) s(-1)) significantly larger than the experimental results. If the torsional mode in the ground state is treated as free internal rotation the preexponential factors reduce significantly, giving excellent agreement with experimental values. The DFT results are in excellent (fortuitous?) agreement with the experimental value for activation energy for 1,2-DCE while the MP2 and HF results seem to overestimate the barrier. However, DFT results for EC is 4.5 kcal mol(-1) less than the previously reported experimental values. At all levels, theory predicts an increase in HCI elimination barrier on beta-Cl substitution on EC.

Trends in consanguineous marriage in Karnataka, South India, 1980–89

Analysis of data on 106,848 marriages in the cities of Bangalore and Mysore, South India, between 1980 and 1989 showed that levels of consanguineous marriage varied between cities through time and by religion. The average coefficient of inbreeding was higher in Bangalore (F = 0·0339) than in Mysore (F = 0·0203), principally reflecting large-scale, post-Independence rural migration into Bangalore. Although there was some evidence of a decline in consanguineous marriages in Mysore, there was no convincing support in either city for earlier projections of a rapid reduction in the popularity of unions between close biological relatives.

Sustainable biomass production for energy in selected Asian countries

This paper presents a synthesis of assessment of sustainable biomass production potential in six Asian countries-China, India, Malaysia, Philippines, Sri Lanka and Thailand, and is based on the detailed studies carried out in these countries under the Asian Regional Research Programme in Energy, Environment and Climate (ARRPEEC). National level studies were undertaken to estimate land availability for biomass production, identify and evaluate the biomass production options in terms of yield per hectare and financial viability, estimate sustainable biomass production for energy, and estimate the energy potential of biomass production in the six Asian countries. Sustainable biomass production from plantation is estimated to be in the range of 182.5-210.5, 62-310, 0.4-1.7, 3.7-20.4, 2.0-9.9 and 11.6-106.6 Mt yr(-1) for China, India, Malaysia, Philippines, Sri Lanka and Thailand, respectively. The maximum annual electricity generation potential, using advanced technologies, from the sustainable biomass production is estimated to be about 27, 114, 4.5, 79, 254 and 195 percentage of the total electricity generation in year 2000 in China, India, Malaysia, Philippines, Sri Lanka and Thailand, respectively. Investment cost for bioenergy production varies from US$381 to 1842 ha(-1) in the countries considered in this study; investment cost for production of biomass varies from US$5.1 to 23 t(-1). (C) 2003 Elsevier Ltd. All rights reserved.

Effect of inorganic ions, H(2)O(2) and pH on the photocatalytic inactivation of Escherichia coli with silver impregnated combustion synthesized TiO(2) catalyst

The photocatalytic antibacterial activity of Ag impregnated combustion synthesized TiO(2) (0.25 g/L) was studied against Escherichia coil in presence of UV irradiation. The effect of various parameters, such as anions, canons, hydrogen peroxide and pH, on the photocatalytic inactivation was investigated. The addition of inorganic ions showed a negative effect on inactivation. Among anions, the presence of chloride ions was observed to have a maximum negative effect and reduced the inactivation considerably. Among cations, the bacterial inactivation reduced significantly in the presence of Ca(2+) ions. Hydrogen peroxide addition in combination with Ag/TiO(2) photocatalysis, however, improved the inactivation. Photocatalysis with high concentration of H(2)O(2) yielded complete bacterial inactivation within few minutes. The photocatalytic inactivation of E. coil was not affected by variation in pH. (C) 2011 Elsevier B.V. All rights reserved.

Confinement-deconfinement transition and spin correlations in a generalized Kitaev model

We present a spin model, namely, the Kitaev model augmented by a loop term and perturbed by an Ising Hamiltonian, and show that it exhibits both confinement-deconfinement transitions from spin liquid to antiferromagnetic/spin-chain/ferromagnetic phases and topological quantum phase transitions between gapped and gapless spin-liquid phases. We develop a fermionic resonating-valence-bonds (RVB) mean-field theory to chart out the phase diagram of the model and estimate the stability of its spin-liquid phases, which might be relevant for attempts to realize the model in optical lattices and other spin systems. We present an analytical mean-field theory to study the confinement-deconfinement transition for large coefficient of the loop term and show that this transition is first order within such mean-field analysis in this limit. We also conjecture that in some other regimes, the confinement-deconfinement transitions in the model, predicted to be first order within the mean-field theory, may become second order via a defect condensation mechanism. Finally, we present a general classification of the perturbations to the Kitaev model on the basis of their effect on it's spin correlation functions and derive a necessary and sufficient condition, within the regime of validity of perturbation theory, for the spin correlators to exhibit a long-ranged power-law behavior in the presence of such perturbations. Our results reproduce those of Tikhonov et al. [Phys. Rev. Lett. 106, 067203 (2011)] as a special case.

The standard enthalpy and entropy of formation of Rh2O3 - A third-law optimization

The standard Gibbs energy of formation of Rh203 at high temperature has been determined recently with high precision. The new data are significantly different from those given in thermodynamic compilations.Accurate values for enthalpy and entropy of formation at 298.15 K could not be evaluated from the new data,because reliable values for heat capacity of Rh2O3 were not available. In this article, a new measurement of the high temperature heat capacity of Rh2O3 using differential scanning calorimetry (DSC) is presented.The new values for heat capacity also differ significantly from those given in compilations. The information on heat capacity is coupled with standard Gibbs energy of formation to evaluate values for standard enthalpy and entropy of formation at 289.15 K using a multivariate analysis. The results suggest a major revision in thermodynamic data for Rh2O3. For example, it is recommended that the standard entropy of Rh203 at 298.15 K be changed from 106.27 J mol-' K-'given in the compilations of Barin and Knacke et al. to 75.69 J mol-' K". The recommended revision in the standard enthalpy of formation is from -355.64 kJ mol-'to -405.53 kJ mol".

Low loss and frequency (1 kHz–1 MHz) independent dielectric characteristics of 3BaO–3TiO2–B2O3 glasses

X-ray powder diffraction along with differential thermal analysis carried out on the as-quenched samples in the 3BaO–3TiO2–B2O3 system confirmed their amorphous and glassy nature, respectively. The dielectric constants in the 1 kHz–1 MHz frequency range were measured as a function of temperature (323–748 K). The dielectric constant and loss were found to be frequency independent in the 323–473 K temperature range. The temperature coefficient of dielectric constant was estimated using Havinga’s formula and found to be 16 ppm K−1. The electrical relaxation was rationalized using the electric modulus formalism. The dielectric constant and loss were 17±0.5 and 0.005±0.001, respectively at 323 K in the 1 kHz–1 MHz frequency range which may be of considerable interest to capacitor industry.

Dielectric properties of Li2O–3B2O3 glasses

The frequency and temperature dependences of the dielectric constant and the electrical conductivity of the transparent glasses in the composition Li2O–3B2O3 were investigated in the 100 Hz–10 MHz frequency range. The dielectric constant and the loss in the low frequency regime were electrode material dependent. Dielectric and electrical relaxations were, respectively, analyzed using the Cole–Cole and electric modulus formalisms. The dielectric relaxation mechanism was discussed in the framework of electrode and charge carrier (hopping of the ions) related polarization using generalized Cole–Cole expression. The frequency dependent electrical conductivity was rationalized using Jonscher’s power law. The activation energy associated with the dc conductivity was 0.80±0.02 eV, which was ascribed to the motion of Li+ ions in the glass matrix. The activation energy associated with dielectric relaxation was almost equal to that of the dc conductivity, indicating that the same species took part in both the processes. Temperature dependent behavior of the frequency exponent (n) suggested that the correlated barrier hopping model was the most apposite to rationalize the electrical transport phenomenon in Li2O–3B2O3 glasses. These glasses on heating at 933 K/10 h resulted in the known nonlinear optical phase LiB3O5.

Bi4Ti3O12–5BiFeO3 Aurivillius intergrowth: Structural and ferroelectric properties

Aurivillus intergrowth Bi4Ti3O12–5BiFeO3 was demonstrated to be ferroelectric that evoked the possibility of achieving high temperature magnetoelectric property in this family of compounds. X-ray diffraction studies confirmed its structure to be orthorhombic [Fmm2; a = 5.5061(11) Å, b = 5.4857(7) Å, c = 65.742(12) Å]. However, transmission electron microscopy established the random incidence of intergrowth at nanoscale corresponding to n = 6 and n = 7 members of the Aurivillius family. Diffuse ferroelectric orthorhombic to paraelectric tetragonal phase transition around 857 K was confirmed by dielectric and high temperature x-ray diffraction studies. Polarization versus electric field hysteresis loops associated with 2Pr of 5.2 μC/cm2 and coercive field of 42 kV/cm were obtained at 300 K.