Structure of the Pyridine-Chloranil Complex in Solution: A Surprise from Depolarized Hyper-Rayleigh Scattering Measurements

In this article, we report the structure of a 1:1 charge transfer complex between pyridine (PYR) and chloranil (CHL) in solution (CHCl(3)) from the measurement of hyperpolarizability (beta(HRS)) and linear and circular depolarization ratios, D and D', respectively, by the hyper-Rayleigh scattering technique and state-of-the-art quantum chemical calculations. Using linearly (electric field vector along X) and circularly polarized incident light, respectively, we have measured two macroscopic depolarization ratios D = I(X,X)(2 omega)/I(X,Z)(2 omega) and D' = I(X,C)(2 omega)/I(Z,C)(2 omega) in the laboratory fixed XYZ frame by detecting the second harmonic (SH) scattered light in a polarization resolved fashion. The stabilization energy and the optical gap calculated through the MP2/cc-pVDZ method using Gaussian09 were not significantly different to distinguish between the cofacial and T-shape structures. Only when the experimentally obtained beta(HRS) and the depolarization ratios, D and D', were matched with the theoretically computed values from single and double configuration interaction (SDCI) calculations performed using the ZINDO-SCRF technique, we concluded that the room temperature equilibrium structure of the complex is cofacial. This is in sharp contrast to an earlier theoretical prediction of the T-shape structure of the complex.

Role of the cesium antimonide layer in the Na2KSb/Cs3Sb photocathode

When radiation of sufficiently high energy is incident on the surface of a semiconductor photocathode, electrons are excited from the valence band to the conduction band and these may contribute to the photocurrent. The photocurrent in a single-layer cathode is found to be small, because of collisions within the cathode material, the electron affinity condition, etc. It is observed that when a thin layer of n-type cesium antimonide (Cs3Sb) is deposited over a p-type layer of sodium potassium antimonide (Na2KSb), there occurs a sharp rise in the photocurrent. The causes for the dramatic increase in the photocurrent obtainable from a sodium potassium antimonide cathode, by depositing a thin layer of cesium antimonide are analyzed in this article. It has been shown that the interface between sodium potassium antimonide and cesium antimonide can result in lowering of the electron affinity to a level below the bottom of the conduction band of sodium potassium antimonide. The drift field that arises at the heterointerface enables the electrons to reach the surface, leading to the emission of almost all the photogenerated electrons within the cathode. The processes involved in photoemission from such a double-layer cathode are examined from a theoretical point of view. The spectral response of the two-layer cathode is also found to be better than that of a single-layer cathode.

Effect of surface on the conductance characteristics of Au���Bi2Sr2CaCu2O8+�� (single crystal) point contact junctions

We report the effect of surface treatments on the dynamic conductance curves (G=dI/dV���V) of Au���Bi2Sr2CaCu2O8+�� (single crystal) point contact junctions of variable junction conductances (100 mS���G���100 ��S). We find that if the crystal surface is cleaved freshly just prior to making contacts, all irreproducible sharp multiple features often observed in tunneling data of Bi(2212) oxide superconductors disappear. If the cleaved crystal surfaces are left under ambient conditions for a few days and the tunneling experiments are repeated, these multiple features reappear. We also find that if the current in the junction is made to pass predominantly through the bulk (and not along the surface), gap features are sharper. The observed conductance curves are fitted to a modified model [G. E. Blonder et al., Phys. Rev. B 25, 4515 (1982)] and estimated gap values are �����28 to 30 meV corresponding to the ratio 2��/kBTc ��� 7.5 with lifetime broadening ��/�����0.2. We conclude that the sharp multiple features observed in Bi(2212) tunneling curves has no intrinsic origin in the bulk and they arise from the surface only.

State of bismuth in BaBiO3 and BaBi1-xPbxO3: Bi���4f photoemission and Bi���L3 absorption spectroscopic studies

The 2p���6d feature in the Bi���L3 spectra has different energies in the semiconducting (0.0���x<0.7) and the superconducting (x=0.75) compositions of BaBi1���xPbxO3. The Bi���4f core level spectrum shows distinct features ascribable to Bi III and Bi V in BaBiO3 and in the semiconducting compositions; the width of the 4f peaks is also considerably larger in these compositions compared to that in BaBi0.25Pb0.75O3, which shows a single sharp Bi���4f feature.

Developments in amplitude-comparator techniques for distance relays

The paper reports the development of new amplitude-comparator techniques which allow the instantaneous comparison of the amplitude of the signals derived from primary line quantities. These techniques are used to derive a variety of impedance characteristics. The merits of the new relaying system are: the simple mode of the relay circuitry, the derivation of closed polar characteristics (i.e. quadrilateral) by a single measuring gate and sharp discontinuities in the polar characteristics. Design principles and circuit models in their schematic form are described and, in addition, a comprehensive theoretical basis for comparison is also presented. Dynamic test results are presented for a quadrilateral characteristic of potentially general application.

Hybrid Comparison Technique for Distance Relays

A new hybrid comparison technique for transmission line protection, providing polar characteristics marked by sharp discontinuities, has been developed. The comparator models, described in block schematic form, accompany a steady state theoretical basis for comparison. Dynamic test results are indicated for a directional quadrilateral characteristic which closely corresponds to the probable fault area of a transmission line.

Transport and infrared photoresponse properties of InN nanorods/Si heterojunction

The present work explores the electrical transport and infrared (IR) photoresponse properties of InN nanorods (NRs)/n-Si heterojunction grown by plasma-assisted molecular beam epitaxy. Single-crystalline wurtzite structure of InN NRs is verified by the X-ray diffraction and transmission electron microscopy. Raman measurements show that these wurtzite InN NRs have sharp peaks E(2)(high) at 490.2 cm(-1) and A(1)(LO) at 591 cm(-1). The current transport mechanism of the NRs is limited by three types of mechanisms depending on applied bias voltages. The electrical transport properties of the device were studied in the range of 80 to 450 K. The faster rise and decay time indicate that the InN NRs/n-Si heterojunction is highly sensitive to IR light.

Particle image velocimetry and infrared thermography in a levitated droplet with nanosilica suspensions

Preferential accumulation and agglomeration kinetics of nanoparticles suspended in an acoustically levitated water droplet under radiative heating has been studied. Particle image velocimetry performed to map the internal flow field shows a single cell recirculation with increasing strength for decreasing viscosities. Infrared thermography and high speed imaging show details of the heating process for various concentrations of nanosilica droplets. Initial stage of heating is marked by fast vaporization of liquid and sharp temperature rise. Following this stage, aggregation of nanoparticles is seen resulting in various structure formations. At low concentrations, a bowl structure of the droplet is dominant, maintained at a constant temperature. At high concentrations, viscosity of the solution increases, leading to rotation about the levitator axis due to the dominance of centrifugal motion. Such complex fluid motion inside the droplet due to acoustic streaming eventually results in the formation of a ring structure. This horizontal ring eventually reorients itself due to an imbalance of acoustic forces on the ring, exposing larger area for laser absorption and subsequent sharp temperature rise.

Structural, dielectric relaxation and piezoelectric characterization of Sr2+ substituted modified PMS-PZT ceramic

Pyrochlore phase free [Pb0.94Sr0.06] [(Mn1/3Sb2/3)(0.05)(Zr0.53Ti0.47)(0.95)] O-3 ceramics has been synthesized with pure Perovskite phase by semi-wet route using the columbite precursor method. The field dependences of the dielectric response and the conductivity have been measured in a frequency range from 50 Hz to 1 MHz and in a temperature range from 303 K to 773 K. An analysis of the real and imaginary parts of the dielectric permittivity with frequency has been performed, assuming a distribution of relaxation times. The scaling behavior of the dielectric loss spectra suggests that the distribution of the relaxation times is temperature independent. The SEM photographs of the sintered specimens present the homogenous structures and well-grown grains with a sharp grain boundary. The material exhibits tetragonal structure. When measured at frequency (100 Hz), the polarization shows a strong field dependence. Different piezoelectric figures of merit (k(p), d(33) and Q(m)) of the material have also been measured obtaining their values as 0.53, 271 pC/N and 1115, respectively, which are even higher than those of pure PZT with morphotropic phase boundary (MPB) composition. Thus the present ceramics have the optimal overall performance and are promising candidates for the various high power piezoelectric applications. (C) 2011 Elsevier B.V. All rights reserved.

Electrical switching and optical studies on amorphous GexSe35-xTe65 thin films

The electrical switching behavior of amorphous GexSe35-xTe65 thin film samples has been studied in sandwich geometry of electrodes. It is found that these samples exhibit memory switching behavior, which is similar to that of bulk Ge-Se-Te glasses. As expected, the switching voltages of GexSe35-xTe65 thin film samples are lower compared to those of bulk samples. In both thin film amorphous and bulk glassy samples, the switching voltages are found to increase with the increase in Ge concentration, which is consistent with the increase in network connectivity with the addition of higher coordinated Ge atoms. A sharp increase is seen in the composition dependence of the switching fields of amorphous GexSe35-xTe65 films above x = 21, which can be associated with the stiffness transition. Further, the optical band gap of a-GexSe35-x Te-65 thin film samples, calculated from the absorption spectra, is found to show an increasing trend with the increase in Ge concentration, which is consistent with the variation of switching fields with composition. The increase in structural cross-linking with progressive addition of 4-fold coordinated Ge atoms is one of the main reasons for the observed increase in switching fields as well as band gaps of GexSe35-xTe65 samples. (C) 2011 Elsevier B.V. All rights reserved.

Effect of dehydration on the mechanical properties of sodium saccharin dihydrate probed with nanoindentation

Nanoindentation is used to explore the variation of mechanical properties associated with the dehydration process in sodium saccharin dihydrate. Upon indenting using a Berkovich tip, (011) and (101) faces exhibit explicit mechanical anisotropy that is consistent with the underlying crystal structure and intermolecular interactions. For freshly grown crystals, (011) is stiffer than (101) by 14%, while (101) is harder than (011) by 8%. Being a heavily hydrated system, the measured mechanical responses contain information pertinent to the fluidity associated with lattice water. Indentation on (011) with a sharp cube-corner tip induces a fluid flow; this observation is uncommon in molecular crystals. The crystals effloresce over a period of time with the generation of a more compact crystal structure and consequently increasing H and E.

Hydration dynamics of protein molecules in aqueous solution: Unity among diversity

Dielectric dispersion and NMRD experiments have revealed that a significant fraction of water molecules in the hydration shell of various proteins do not exhibit any slowing down of dynamics. This is usually attributed to the presence of the hydrophobic residues (HBR) on the surface, although HBRs alone cannot account for the large amplitude of the fast component. Solvation dynamics experiments and also computer simulation studies, on the other hand, repeatedly observed the presence of a non-negligible slow component. Here we show, by considering three well-known proteins (lysozyme, myoglobin and adelynate kinase), that the fast component arises partly from the response of those water molecules that are hydrogen bonded with the backbone oxygen (BBO) atoms. These are structurally and energetically less stable than those with the side chain oxygen (SCO) atoms. In addition, the electrostatic interaction energy distribution (EIED) of individual water molecules (hydrogen bonded to SCO) with side chain oxygen atoms shows a surprising two peak character with the lower energy peak almost coincident with the energy distribution of water hydrogen bonded to backbone oxygen atoms (BBO). This two peak contribution appears to be quite general as we find it for lysozyme, myoglobin and adenylate kinase (ADK). The sharp peak of EIED at small energy (at less than 2 k(B)T) for the BBO atoms, together with the first peak of EIED of SCO and the HBRs on the protein surface, explain why a large fraction (similar to 80%) of water in the protein hydration layer remains almost as mobile as bulk water Significant slowness arises only from the hydrogen bonds that populate the second peak of EIED at larger energy (at about 4 k(B)T). Thus, if we consider hydrogen bond interaction alone, only 15-20% of water molecules in the protein hydration layer can exhibit slow dynamics, resulting in an average relaxation time of about 5-10 ps. The latter estimate assumes a time constant of 20-100 ps for the slow component. Interestingly, relaxation of water molecules hydrogen bonded to back bone oxygen exhibit an initial component faster than the bulk, suggesting that hydrogen bonding of these water molecules remains frustrated. This explanation of the heterogeneous and non-exponential dynamics of water in the hydration layer is quantitatively consistent with all the available experimental results, and provides unification among diverse features.

High sensitivity low field magnetically gated resistive switching in CoFe2O4/La0.66Sr0.34MnO3 heterostructure

The phenomenon of resistive switching (RS) has been demonstrated in several non-magnetic and some magnetic oxide systems, however the ``magnetic'' aspect of magnetic oxides has not been emphasized especially in terms of low field tunability. In our work, we examined the CoFe2O4/La0.66Sr0.34MnO3 all-magnetic oxide interface system for RS and discovered a very sharp (bipolar) transition at room temperature that can be gated with high sensitivity by low magnetic fields (similar to 0-100 mT). By using a number of characterizations, we show that this is an interface effect, which may open up interesting directions for manipulation of the RS phenomenon. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4707373]

Anomalous low-temperature magnetic and magnetotransport properties in Ru-deficient SrRuO3

SrRuO3 is a well-known itinerant ferromagnet with many intriguing characteristics. The Ru deficiency in this system is believed to play a pivotal role in influencing many of its magnetic and transport properties. The present study involves the magnetic and transport properties of the Ru-deficient SrRu0.93O3 sample to gain more insight into the unusual low-temperature behavior. The ac susceptibility study reveals a sharp ferromagnetic transition at 150 K followed by a hump at T-h similar to 50 K, which has anomalous frequency dependence. Besides, the T-h shifts to lower temperatures with an increase in the superposed dc-biasing field and adheres to H-2 dependence, in accordance with the Gabay and Toulouse line for the Heisenberg spin glass systems. We also observe a pronounced memory effect toward the low-temperature side, signifying the characteristic of glassy behavior. The temperature-dependent magnetoresistance indicates the signature of an additional ordering toward the low-temperature side. All of the interesting findings combined unveil the existence of low-temperature cryptic magnetic phase in SrRu0.93O3. (C) 2012 American Institute of Physics. doi:10.1063/1.3673427]

Superconducting fluctuations and anomalous phonon renormalization much above superconducting transition temperature in Ca4Al2O5.7Fe2As2

Raman studies on Ca4Al2O5.7Fe2As2 superconductor in the temperature range of 5K to 300 K, covering the superconducting transition temperature T-c = 28.3 K, reveal that the Raman mode at similar to 230 cm(-1) shows a sharp jump in frequency by similar to 2% and linewidth increases by similar to 175% at T-o similar to 60 K. Below T-o, anomalous softening of the mode frequency and a large decrease by similar to 10 cm(-1) in the linewidth are observed. These precursor effects at T-0 (similar to 2T(c)) are attributed to significant superconducting fluctuations, possibly enhanced due to reduced dimensionality arising from weak coupling between the well separated (similar to 15 angstrom) Fe-As layers in the unit cell. A large blue-shift of the mode frequency between 300 K and 60 K (similar to 7%) indicates strong spin-phonon coupling in this superconductor. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4724206]