The dynamics of solvation of an electron in the image potential state by a layer of polar adsorbates

Recently, ultrafast two-photon photoemission has been used to study electron solvation at a two-dimensional metal/polar adsorbate interfaces [A. Miller , Science 297, 1163 (2002)]. The electron is bound to the surface by the image interaction. Earlier we have suggested a theoretical description of the states of the electron interacting with a two-dimensional layer of the polar adsorbate [K. L. Sebastian , J. Chem. Phys. 119, 10350 (2003)]. In this paper we have analyzed the dynamics of electron solvation, assuming a trial wave function for the electron and the solvent polarization and then using the Dirac-Frenkel variational method to determine it. The electron is initially photoexcited to a delocalized state, which has a finite but large size, and causes the polar molecules to reorient. This reorientation acts back on the electron and causes its wave function to shrink, which will cause further reorientation of the polar molecules, and the process continues until the electron gets self-trapped. For reasonable values for the parameters, we are able to obtain fair agreement with the experimental observations. (c) 2005 American Institute of Physics.

Ribosome-RNA interaction: a potential target for developing antiviral against hepatitis C virus

Hepatitis C virus (HCV), a member of Flaviviridae, encoding a positive-sense single-stranded RNA translates by cap-independent mechanism using the internal ribosome entry site (IRES) present in the 5' UTR of the virus. The IRES has complex stem loop structures and is capable of recruiting the 40S ribosomal subunit in a factor-independent fashion. As the IRES sequence is highly conserved throughout the HCV genotypes and the translation is the first obligatory step of the HCV life cycle, the IRE'S-mediated translation, or more specifically, the ribosome HCV RNA interaction is an attractive target to design effective antivirals. This article will focus on the mechanism of the HCV IRES translation and the various ways in which the interaction of ribosome and IRES has been targeted.

Electrocatalysis and redox behavior of Pt(2+) ion in CeO(2) and Ce(0.85)Ti(0.15)O(2): XPS evidence of participation of lattice oxygen for high activity

Electronic states of CeO(2), Ce(1 -aEuro parts per thousand x) Pt (x) O(2 -aEuro parts per thousand delta) , and Ce(1 -aEuro parts per thousand x -aEuro parts per thousand y) Ti (y) Pt (x) O(2 -aEuro parts per thousand delta) electrodes have been investigated by X-ray photoelectron spectroscopy as a function of applied potential for oxygen evolution and formic acid and methanol oxidation. Ionically dispersed platinum in Ce(1 -aEuro parts per thousand x) Pt (x) O(2 -aEuro parts per thousand delta) and Ce(1 -aEuro parts per thousand x -aEuro parts per thousand y) Ti (y) Pt (x) O(2 -aEuro parts per thousand delta) is active toward these reactions compared with CeO(2) alone. Higher electrocatalytic activity of Pt(2+) ions in CeO(2) and Ce(1 -aEuro parts per thousand x) Ti (x) O(2) compared with the same amount of Pt(0) in Pt/C is attributed to Pt(2+) ion interaction with CeO(2) and Ce(1 -aEuro parts per thousand x) Ti (x) O(2) to activate the lattice oxygen of the support oxide. Utilization of this activated lattice oxygen has been demonstrated in terms of high oxygen evolution in acid medium with these catalysts. Further, ionic platinum in CeO(2) and Ce(1 -aEuro parts per thousand x) Ti (x) O(2) does not suffer from CO poisoning effect unlike Pt(0) in Pt/C due to participation of activated lattice oxygen which oxidizes the intermediate CO to CO(2). Hence, higher activity is observed toward formic acid and methanol oxidation compared with same amount of Pt metal in Pt/C.

t-Na-2(VO)P2O7: A 3.8 V Pyrophosphate Insertion Material for Sodium-Ion Batteries

Pyrophosphate oxyanionic framework compounds offer a great platform to investigate new battery materials. In our continuing effort to explore pyrophosphate cathodes for sodium-ion batteries, we report, for the first time, the synthesis and use of tetragonal Na-2(VO)P2O7 as a potential sodium-ion insertion material. This material can be easily prepared by using a conventional solid-state route at a relatively low temperature of 400 degrees C. Stabilizing as a tetragonal structure with an open framework, the material offers pathways for Na+ diffusion. The as-synthesized material, with no further cathode optimization, yields a reversible capacity (Q) approaching 80 mAh g(-1) (Q(Theoretical) = 93.4 mAh g(-1)) involving a one electron V5+/V4+ redox potential located at 3.8 V (vs. Na/Na+). Furthermore, the material exhibits decent rate kinetics and reversibility. Combining green synthesis and moderate electrochemical properties, t-Na-2(VO)P2O7 is reported as a new addition to the growing family of pyrophosphate cathodes for sodium-ion batteries.

The Electronic Structure of Graphite from Compton Profile Measurements

Compton profile data are used to investigate the ground state wavefunction of graphite. The results of two new $\gamma$-ray measurements are reported and compared with the results of earlier $\gamma$-ray and electron scattering measurements. A tight-binding calculation has been carried out and the results of earlier calculations based on a molecular model and a pseudo-potential wavefunction are considered. The analysis, in terms of the reciprocal form factor, shows that none of the calculations gives an adequate description of the data in the basal plane although the pseudo-potential calculation describes the anisotropy in the plane reasonably well. In the basal plane the zero-crossing theorem appears to be violated and this problem must be resolved before more accurate models can be derived. In the c-axis direction the molecular model and the tight binding calculation give better agreement with the experimental data than does the pseudopotential calculation.

Plasma diagnostics of the high pressure oxygen-sputtering process

The characteristics of the high pressure oxygen-sputtering plasma in the pressure range 0.8–2.4 mbar have been studied using the Langmuir probe technique. The variation in plasma parameters such as positive ion density, electron density, mean electron energy and floating potential with pressure and temperature has been investigated. It has been observed that the positive ion density increases at high substrate temperatures whereas the negative ion density decreases. The study of the variation in mean electron energy and floating potential also indicated the possibility that the number of negative ions is less when the substrates are at elevated temperatures. Since the negative ions are supposed to cause re-sputtering and make the films off-stoichiometric, the reduction in the negative ion density as observed at elevated substrate temperatures is better suited for depositing stoichiometric YBa2Cu3O7−δ superconducting thin films.

Pressure induced phase transition in metallic LaB6: A Raman study

We report high pressure Raman studies on single crystals of metallic LaB6 upto a pressure of 16.$ GPa. Raman spectra shows three lines at 680 cm(-1) (T-2g), 1120 cm(-1) (E-g) and 1258 cm(-1) (A(1g)), associated with the internal modes of B-6 molecule. The T-2g mode shows an asymmetric Fano line shape, arising from the interference between the phonon line and the electronic continuum. The line is fitted with I(omega) = I-0(q + epsilon(2))/(I + epsilon(2)) where epsilon = (omega - omega(0))/Gamma, omega(0) is the phonon frequency renormalised due to electron-phonon self energy corrections, Tis the width parameter proportional to the square of the matrix element of the electron-phonon interaction potential. The parameter a signifies the strength of interference. Most interestingly our pressure data for the T-2g mode shows a significant change in the slope of the mode frequency with pressure d omega(0)/dP and Gamma at 9.5 GPa. This clearly indicates that LaB6 undergoes a subtle phase transition at 9.5 GPa within the metallic phase.

Characterization of Interactions Involving Bromine in 2,2-Dibromo2,3-dihydroinden-1-one via Experimental Charge Density Analysis

Experimental and theoretical charge density analyses on 2,2-dibromo-2,3-dihydroinden-1-one have been carried out to quantify the topological features of a short CBr....O halogen bond with nearly linear geometry (2.922 angstrom, angle CBr....O = 172.7 degrees) and to assess the strength of the interactions using the topological features of the electron density. The electrostatic potential map indicates the presence of the s-hole on bromine, while the interaction energy is comparable to that of a moderate OH....O hydrogen bond. In addition, the energetic contribution of CH.....Br interaction is demonstrated to be on par with that of the CBr....O halogen bond in stabilizing the crystal structure.

Surface chemical studies on mica and galena using dextrin

The interactions of dextrin with biotite mica and galena have been investigated through adsorption, flotation, and electrokinetic measurements. The adsorption densities of dextrin onto mica continuously increase with increase of pH, while those onto galena show a maximum at pH 11.5. It is observed that the adsorption density of dextrin onto galena is quite high compared to that on mica. Both the adsorption isotherms exhibit Langmuirian behavior. Electrokinetic measurements portray conformational rearrangements of macromolecules with the loading, resulting in a shift of the shear plane, further away from the interface. Dissolution experiments indicate release of the lattice metal ions from mica and galena. Coprecipitation tests confirm polymer-metal ion interaction in the bulk solution. Dextrin does not exhibit any depressant action toward mica, whereas, with galena, the flotation recovery is decreased with an increase in pH beyond 9, in the presence of dextrin, complementing the adsorption results. Differential flotation results on a synthetic mixture of mica and galena show that mica can be selectively separated from galena using dextrin as a depressant for galena above pH 10. Possible mechanisms of interaction between dextrin and mica/galena are discussed.

Enhancing field emission from a carbon nanotube array by lateral control of electrodynamic force field

Fluctuation of field emission current from carbon nanotubes (CNTs) poses certain difficulties for their use in nanobiomedical X-ray devices and imaging probes. This problem arises due to deformation of the CNTs due to electrodynamic force field and electron-phonon interaction. It is of great importance to have precise control of emitted electron beams very near the CNT tips. In this paper, a new array configuration with stacked array of CNTs is analysed and it is shown that the current density distribution is greatly localised at the middle of the array, that the scatter due to electrodynamic force field is minimised and that the temperature transients are much smaller compared to those in an array with random height distribution.

Universal jellium BCS picture for Peierls and spin-Peierls phase transitions

Both metal-insulator Peierls and antiferromagnetic spin-Peierls dimerized phase transitions are observed to have a BCS electron-phonon interaction parameter which is compatible with the jellium value λ = 2/3π ≈ 0.21.

Intrinsic two-phonon-exchange mechanism of superconductivity and enhancement of Tc

It is shown that the intrinsic two-phonon terms occurring in first order in the electron-phonon interaction Hamiltonian can give rise to (i) an essential doubling of the interaction phase space (BCS cutoff) and (ii) an attractive pairing interaction proportional to the phonon occupation numbers. This suggests a possible enhancement of the superconductive transition temperature in the presence of high-frequency acoustic field.

Large-amplitude chirped coherent phonons in tellurium mediated by ultrafast photoexcited carrier diffusion

We report femtosecond time-resolved reflectivity measurements of coherent phonons in tellurium performed over a wide range of temperatures (3-296 K) and pump-laser intensities. A totally symmetric A(1) coherent phonon at 3.6 THz responsible for the oscillations in the reflectivity data is observed to be strongly positively chirped (i.e., phonon time period decreases at longer pump-probe delay times) with increasing photoexcited carrier density, more so at lower temperatures. We show that the temperature dependence of the coherent phonon frequency is anomalous (i.e, increasing with increasing temperature) at high photoexcited carrier density due to electron-phonon interaction. At the highest photoexcited carrier density of (1.4 x 10(21) cm(-3) and the sample temperature of 3 K, the lattice displacement of the coherent phonon mode is estimated to be as high as similar to 0.24 angstrom. Numerical simulations based on coupled effects of optical absorption and carrier diffusion reveal that the diffusion of carriers dominates the nonoscillatory electronic part of the time-resolved reflectivity. Finally, using the pump-probe experiments at low carrier density of 6 x 10(18) cm(-3), we separate the phonon anharmonicity to obtain the electron-phonon coupling contribution to the phonon frequency and linewidth.

Lattice embedding and equilibrium geometry of metal-halogen chains in the two-band extended Hubbard model

Two-band extended Hubbard model studies show that the shift in optical gap of the metal-halogen (MX) chain upon embedding in a crystalline environment depends upon alternation in the site-diagonal electron-lattice interaction parameter (epsilon(M)) and the strength of electron-electron interactions at the metal site (U(M)). The equilibrium geometry studies on isolated chains show that the MX chains tend to distort for alternating epsilon(M) and small U(M) values.