Free Energy Gap Dependence of the Electron-Transfer Rate from the Inverted to the Normal Region

numerical study of the free energy gap (FEG) dependence of the electron-transfer rate in polar solvents is presented. This study is based on the generalized multidimensional hybrid model, which not only includes the solvent polarization and the molecular vibration modes, but also the biphasic polar response of the solvent. The free energy gap dependence is found to be sensitive to several factors, including the solvent relaxation rate, the electronic coupling between the surfaces, the frequency of the high-frequency quantum vibrational mode, and the magnitude of the solvent reorganization energy. It is shown that in some cases solvent relaxation can play an important role even in the Marcus normal regime. The minimal hybrid model involves a large number of parameters, giving rise to a diverse non-Marcus FEG behavior which is often determined collectively by these parameters. The model gives the linear free energy gap dependence of the logarithmic rate over a substantial range of FEG, spanning from the normal to the inverted regime. However, even for favorable values of the relevant parameters, a linear free energy gap dependence of the rate could be obtained only over a range of 5000-6000 cm(-1) (compared to the experimentally observed range of 10000 cm(-1) reported by Benniston et al.). The present work suggests several extensions/generalizations of the hybrid model which might be necessary to fully understand the observed free energy gap dependence.

Studies on the target conditioning for deposition of $LiCoO_{2}$ films

Deposition of good quality thin films of Lithium Cobalt Oxide (LiCoO2), by sputtering is preceded by target conditioning, which dictates the surface composition, morphology and electrochemical performance of the deposited film. Sputtering from a Virgin target surface, results in films with excess of the more reactive elements. The concentration of these reactive elements in the films decreases until the system reaches a steady state after sufficient sputtering from the target. This paper discusses the deposition kinetics in terms of target conditioning of LiCoO2. The composition, morphology and texturing of deposited film during various hours of sputtering were analyzed using X-ray photoelectron Spectroscopy (XPS) and Field Emission Scanning electron microscopy (FESEM). The compositional stability is not observed in the films formed during the initial hours or Sputtering from the fresh target, which becomes stable after several hours of sputtering. The Li and Co concentration in the Films deposited subsequently is found to be varying and possible causes are discussed. After the compositional stability is reached, electrochemical analysis of LiCoO2 thin films was performed, which shows a discharge capacity of 129 mu Ah/cm(2).

Ground and Excited State Intramolecular Proton Transfer in Salicylic Acid: an Ab Initio Electronic Structure Investigation

Energetics of the ground and excited state intramolecular proton transfer in salicylic acid have been studied by ab initio molecular orbital calculations using the 6-31G** basis set at the restricted Hartree-Fock (RHF) and configuration interaction-single excitation (CIS) levels and also using the semiempirical method AM1 at the RHF level as well as with single and pair doubles excitation configuration interaction spanning eight frontier orbitals (PECI = 8). The ab initio potential energy profile for intramolecular proton transfer in the ground state reveals a single minimum corresponding to the primary form, in the first excited singlet state, however, there are two minima corresponding to the primary and tautomeric forms, separated by a barrier of similar to 6 kcal/mol, thus accounting for dual emission in salicylic acid. Electron density changes with electronic excitation and tautomerism indicate no zwitterion formation. Changes in spectral characteristics with change in pH, due to protonation and deprotonation of salicylic acid, are also accounted for, qualitatively. Although the AM1 calculations suggest a substantial barrier for proton transfer in the ground as well as the first excited state of SA, it predicts the transition wavelength in near quantitative accord with the experimental results for salicylic acid and its protonated and deprotonated forms.

Tungsten(0)-carbonyl complexes of naphthylazoimidazoles

The reaction of W(CO)(6) with 1-alkyl-2-(naphthyl-alpha-azo)imidazole (alpha-NaiR) has synthesized [W(CO)(5)(alpha-NaiR-N)] (alpha-NaiR-N refers to the monodentate imidazole-N donor ligand) at room temperature. The structure of[W(CO)(5)(alpha-NaiMe-N)] shows a monodentate imidazole-N coordination of 1-methyl-2-(naphthyl-alpha-azo)imidazole (alpha-NaiMe). The complexes are characterized by elemental, mass and other spectroscopic data (IR, UV-Vis, NMR). On refluxing in THF at 323 K, [W(CO)(5)(alpha-NaiR-N)] undergoes decarbonylation to give [W(CO)(4)(alpha-NaiR-N,N')] (alpha-NaiR-N,N' refers to the imidazole-N(N), azo-N(N') bidentate chelator). Cyclic voltammetry shows metal oxidation (W-0/W-1) and ligand reductions (azo/azo(-), azo(-)/azo(=)). The redox and electronic properties are explained by theoretical calculations using an optimized geometry. DFT computation of [W(CO)(5)(alpha-NaiMe-N)] suggests that the major contribution to the HOMO/HOMO - 1 come from W cl-orbitals and the orbitals of CO. The LUMOs are occupied by alpha-NaiMe functions. The back bonding interaction thus originates from the W(CO)(n) moiety to the LUMO of alpha-NaiR. A TD-DFT calculation has ascribed that HOMO/HOMO - 1 -> LUMO is a mixture of metal-to-ligand and ligand-to-ligand charge transfer underlying the CO -> azoimine contribution. The complexes show emission spectra at room temperature. [W(CO)(4)(alpha-NaiR-N,N')] shows a higher fluorescence quantum yield (phi = 0.05-0.07) than [W(CO)(5)(alpha-NaiR-N)] (phi = 0.01-0.02). (C) 2008 Elsevier Ltd. All rights reserved.

In situ transmission electron microscopy study of deformation of an aluminum alloy tribolayer

Nanoscale deformation in the tribolayer of an Al–Mg alloy is studied using an in situ mechanical probe in a transmission electron microscope. The sample is strained locally at room temperature and the deformation is observed in real time. It is observed that when the tungsten probe comes into contact with the tribolayer, the material exhibits further hardening followed by material removal.

Magnetization, magnetotransport and electron magnetic resonance studies of nanoparticles and nanowires of Pr0.5Sr0.5MnO3

In this paper, we present the preparation and characterization of nanoparticles and nanowires of Pr0.5Sr0.5MnO3 (PSMO). The main results of this investigation are as follows: (a) a comparison with the properties of the bulk material shows that the ferromagnetic (FM) transition at 270 K remains unaffected but the anti-ferromagnetic (AFM) transition at TN = 150 K disappears in the nanoparticles, (b) the size induced ground state magnetic phase (below 150 K) is predominantly FM, coexisting with a residual AFM phase, and (c) the temperature dependence of magnetic anisotropy shows complex behaviour, being higher in the nanoparticles at high temperatures and lower at moderately lower temperatures in comparison with the bulk. The results obtained from the extensive magnetization, magnetotransport and electron magnetic resonance studies made on various samples are presented and discussed in detail.

Synthesis and magnetic studies of flower-like nickel nanocones

Flower-like nickel nanocone structures are synthesized by a simple chemical reduction method using hydrazine hydrate as the reducing agent. The structure, morphology and magnetic properties of as synthesized products are studied by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and SQUID magnetometer. The morphology evolution is studied by varying the reaction temperature and concentration of nickel chloride keeping other conditions unchanged.

Nanocrystalline Janus films of inorganic materials prepared at the liquid-liquid interface

The interface between toluene and water has been employed to prepare ultrathin Janus nanocrystalline films of metal oxides, metal chalcogenides and gold, wherein the surface on the organic-side is hydrophobic and the aqueous-side is hydrophilic. We have changed the nature of the metal precursor or capping agent in the organic layer to increase the hydrophobicity. The strategy employed for this purpose is to increase the length of the alkane chain in the precursor or use a perfluroalkane derivative as precursor or as a capping agent. The hydrophobicity and hydrophilicity of the Janus films have been determined by contact angle measurements. The morphology of hydrophobic and hydrophilic sides of the film have been examined by field emission scanning electron microscopy.

Remarkable Capacity Retention of Nanostructured Manganese Oxide upon Cycling as an Electrode Material for Supercapacitor

Electrochemical capacity retention of nearly X-ray amorphous nanostructured manganese oxide (nanoMnO2) synthesized by mixing directly KMnO4 with ethylene glycol under ambient conditions for supercapacitor studies is enhanced significantly. Although X-ray diffraction (XRD) pattern of nanoMnO2 shows poor crystallinity, it is found that by Mn K-edge X-ray absorption near edge structure (XANES) measurement that the nanoMnO2 obtained is locally arranged in a δ-MnO2-type layered structure composed of edge-shared network of MnO6 octahedra. Field emission scanning electron microscopy and XANES measurements show that nanoMnO2 contains nearly spherical shaped morphology with δ-MnO2 structure, and 1D nanorods of α-MnO2 type structure (powder XRD) in the annealed (600 °C) sample. Volumetric nitrogen adsorption−desorption isotherms, inductively coupled plasma analysis, and thermal analysis are carried out to obtain physicochemical properties such as surface area (230 m2 g−1), porosity of nanoMnO2 (secondary mesopores of diameter 14.5 nm), water content, composition, etc., which lead to the promising electrochemical properties as an electrode for supercapacitor. The nanoMnO2 shows a very high stability even after 1200 cycles with capacity retention of about 250 F g−1.

Analysis Of The Energy Quantization Effects On Single Electron Inverter Performance Through Noise Margin Modeling

Possible integration of Single Electron Transistor (SET) with CMOS technology is making the study of semiconductor SET more important than the metallic SET and consequently, the study of energy quantization effects on semiconductor SET devices and circuits is gaining significance. In this paper, for the first time, the effects of energy quantization on SET inverter performance are examined through analytical modeling and Monte Carlo simulations. It is observed that the primary effect of energy quantization is to change the Coulomb Blockade region and drain current of SET devices and as a result affects the noise margin, power dissipation, and the propagation delay of SET inverter. A new model for the noise margin of SET inverter is proposed which includes the energy quantization effects. Using the noise margin as a metric, the robustness of SET inverter is studied against the effects of energy quantization. It is shown that SET inverter designed with CT : CG = 1/3 (where CT and CG are tunnel junction and gate capacitances respectively) offers maximum robustness against energy quantization.

Graphene, the new nanocarbon

Graphene is a fascinating new nanocarbon possessing, single-, bi- or few- (<= ten) layers of carbon atoms forming six-membered rings. Different types of graphene have been investigated by X-ray diffraction, atomic force microscopy, transmission electron microscopy, scanning tunneling microscopy and Raman spectroscopy. The extraordinary electronic properties of single-and bi-layer graphenes are indeed most unique and unexpected. Other properties of graphene such as gas adsorption characteristics, magnetic and electrochemical properties and the effects of doping by electrons and holes are equally noteworthy. Interestingly, molecular charge-transfer also markedly affects the electronic structure and properties of graphene. Many aspects of graphene are yet to be explored, including synthetic strategies which can yield sufficient quantities of graphene with the desired number of layers.

Synthesis and magnetic studies of flower-like nickel nanocones

Flower-like nickel nanocone structures are synthesized by a simple chemical reduction method using hydrazine hydrate as the reducing agent. The structure, morphology and magnetic properties of as synthesized products are studied by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and SQUID magnetometer. The morphology evolution is studied by varying the reaction temperature and concentration of nickel chloride keeping other conditions unchanged.

A comparative Raman study of the interaction of electron donor and acceptor molecules with graphene prepared by different methods

Interaction of tetrathiafulvalene (TTF) and tetracyanoethylene (TCNE) with few-layer graphene samples prepared by the exfoliation of graphite oxide (EG), conversion of nanodiamond (DG) and arc-evaporation of graphite in hydrogen (HG) has been investigated by Raman spectroscopy to understand the role of the graphene surface. The position and full-width at half maximum of the Raman G-band are affected on interaction with TTF and TCNE and the effect is highest with EG and least with HG. The effect of TTF and TCNE on the 2D-band is also maximum with EG. The magnitude of interaction between the donor/acceptor molecules varies in the same order as the surface areas of the graphenes. (C) 2009 Published by Elsevier B. V.

pi-conjugation and conformation in a semiconducting polymer: small angle x-ray scattering study

Small angle x-ray scattering (SAXS) in a poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) solution has shown the important role of pi-electron conjugation in controlling the chain conformation and assembly. By increasing the extent of conjugation from 30 to 100%, the persistence length (l(p)) increases from 20 to 66 angstrom. Moreover, a pronounced second peak in the pair distribution function has been observed in a fully conjugated chain, at larger length scales. This feature indicates that the chain segments tend to self-assemble as the conjugation along the chain increases. Xylene enhances the rigidity of the PPV backbone to yield extended structures, while tetrahydrofuran solvates the side groups to form compact coils in which the lp is much shorter.