Effect of Pr-Ca substitution on the transport and magnetic behavior of LaMnO3 perovskite

The effect of simultaneous substitution of a fluctuating cation and a divalent cation in LaMnO₃ perovskite modifies the properties of the material to exhibit large valence colossal magnetoresistance (CMR) effect. A good example of these properties is (La_1−2x Pr _x Ca _x )MnO₃ (LPCMO) type CMR material. In this communication it is reported that, with the increase in x (for x=0.1, 0.15, 0.2), the T _c varies between 100 and 120 K with improvisation in metal-insulator transition. Interestingly, resistance increases with x from few hundred ohms to few kilo ohms with corresponding decrease in the unit cell volume. The results of the studies using X-ray diffraction (XRD), electrical resistivity, magnetoresistance and ac susceptibility measurements on LPCMO samples for understanding the structural, transport and magnetic properties are discussed in detail.     

The role of an interface in stabilizing reaction intermediates for hydrogen evolution in aprotic electrolytes

By combining idealized experiments with realistic quantum mechanical simulations of an interface, we investigate electro-reduction reactions of HF, water and methanesulfonic acid (MSA) on the single crystal (111) facets of Au, Pt, Ir and Cu in organic aprotic electrolytes, 1 M LiPF₆ in EC/EMC 3:7W (LP57), the aprotic electrolyte commonly used in Li-ion batteries, 1 M LiClO₄ in EC/EMC 3:7W and 0.2 M TBAPF₆ in 3 : 7 EC/EMC. In our previous work, we have established that LiF formation, accompanied by H₂ evolution, is caused by a reduction of HF impurities and requires the presence of Li at the interface, which catalyzes the HF dissociation. In the present paper, we find that the measured potential of the electrochemical response for these reduction reactions correlates with the work function of the electrode surfaces and that the work function determines the potential for Li⁺ adsorption. The reaction path is investigated further by electrochemical simulations suggesting that the overpotential of the reaction is related to stabilizing the active structure of the interface having adsorbed Li⁺. Li⁺ is needed to facilitate the dissociation of HF which is the source of protons. Further experiments on other proton sources, water and methanesulfonic acid, show that if the hydrogen evolution involves negatively charged intermediates, F⁻ or HO⁻, a cation at the interface can stabilize them and facilitate the reaction kinetics. When the proton source is already significantly dissociated (in the case of a strong acid), there is no negatively charged intermediate and thus the hydrogen evolution can proceed at much lower overpotentials. This reveals a situation where the overpotential for electrocatalysis is related to stabilizing the active structure of the interface, facilitating the reaction rather than providing the reaction energy.

By combining idealized experiments with realistic quantum mechanical simulations of an interface, we investigate electroreduction reactions of HF, water and methanesulfonic acid on the single crystal (111) facets of Au, Pt, Ir and Cu in a variety of aprotic electrolytes.     

Promotion of the oxidation of carbon monoxide at stepped platinum single-crystal electrodes in alkaline media by lithium and beryllium cations

The role of alkali cations (Li(+), Na(+), K(+), Cs(+), and Be(2+)) on the blank voltammetric response and the oxidative stripping of carbon monoxide from stepped Pt single-crystal electrodes in alkaline media has been investigated by cyclic voltammetry. A strong influence of the nature of the cation on both the blank voltammetric profile and the CO oxidation is observed and related to the influence of the cation on the specific adsorption of OH on the platinum surface. Especially Li(+) and Be(2+) cations markedly affect the adsorption of OH and thereby have a significant promoting effect on CO(ads) oxidation. The voltammetric experiments suggest that, on Pt(111), the influence of Li(+) (and Be(2+)) is primarily through a weakening of the repulsive interactions between the OH in the OH adlayer, whereas in the presence of steps also, the onset of OH adsorption is at a lower potential, both on steps and on terraces.     

Cr(VI) Oxidation of Cholesterol—A Kinetic Study Using N-Cetylpicolinium Dichromates,A Class of Novel Phase Transfer Oxidants

Kinetics and Catalysis - Kinetic study of cholesterol oxidation has been studied using a series of N-cetylpicolinium dichromates (CPDC), a class of phase transfer oxidants, in acetic acid medium...     

Elastic properties of the Ta–V system: bcc Ta0.33V0.67 and C15 TaV2

Resonant ultrasound spectroscopy was used to measure the elastic constants of bcc Ta_0.33V_0.67 over the temperature range 3.5–300?K; the results were compared to earlier measurements on C15 TaV₂. The temperature dependence of the polycrystalline shear modulus is completely different in the two phases; that of the bcc phase decreases with temperature whereas that of the C15 phases increases in an anomalous fashion. This difference is consistent with a model involving doubly-degenerate levels at the X point of the Brillouin zone in the C15 phase with the Fermi level lying near the doubly degenerate level. This model accounted for the unusual behaviour of the C15 phase. Debye temperatures were determined from the ultrasonic measurements: 295?K for the C15 phase and 315?K for the bcc phase.     

Irradiation of a cone by a magnetic dipole

Th electromagnetic field produced by a magnetic dipole in thepresence of a perfectly conducting cone of arbitrary cross-sectionis determined. The solution is used to find out how a currenton the cone travelling towards the apex is reflected. Some valuesof the reflection coefficient are calculated. In particular,it is shown that there is a sort of resonance with the reflectionincreasing significantly as the cone approaches a plane.