Dependence of the strength of interaction of carbon monoxide with transition metal clusters on the cluster size

The interaction of CO with Cu, Pd, and Ni at different coverages of the metals on solid substrates has been investigated by He II and core-level spectroscopies, after the nature of variation of the metal core-level binding energies with the coverage or the cluster size is established. The separation between the (1 pi + 5 sigma) and 4 sigma levels of CO increases with a decrease in the size of the metal clusters, accompanied by an increase in the desorption temperature. In the case of Cu, the intramolecular shakeup satellite of CO disappears on small clusters. More importantly, CO dissociates on small Ni clusters, clearly confirming that metal-CO interaction strength increases with a decrease in the cluster size.

Diffusion of sorbates in zeolites Y and A novel dependence on sorbate size and strength of sor ba t e-Zeoli t e interaction

A systematic investigation of monatomic spherical sorbates in the supercages of zeolites Y and A by molecular dynamics technique is presented. Rates of intercage diffusion, rates of cage visits, and the diffusion coefficients have been calculated as a function of the sorbate-zeolite interaction strength. These properties exhibit markedly different dependences on interaction strength for the two zeolites. The observed behavior is shown to be a consequence of the two principal mechanisms of intercage diffusion and the energetic barrier associated with them. The diffusion coefficient and other properties associated with intercage diffusion are found to be directly proportional to the reciprocal of the square of the sorbate diameter when the sorbate diameter is significantly smaller than the window diameter. As the sorbate diameter increases, a peak is observed in all the transport properties investigated including the diffusion coefficient. We call this surprising effect as the ring or levitation effect and it explains several anomalous results reported in the literature and suggests a breakdown of the geometrical criterion for diffusion of sorbates. It shows that under certain conditions nongeometrical factors play a major role and geometrical factors become secondary in the determination of the molecular sieve property. A generalized parameter has been proposed which suggests conditions under which one can expect the ring or levitation effect in any porous medium. Inverse size selectivity becomes operative under these conditions.

Electrical switching studies on Ge-Te-Tl chalcogenide glasses: Effect of thallium on the composition dependence of switching voltages

Bulk Ge(17)Te83_,JI glasses (05x.5_13), have been found to exhibit memory type electrical switching. The switching voltages (also known as threshold voltage V-th) of Ge17Te83-xTlx glasses are found to decrease with increasing thallium content. The rate of decrease of Vtry is greater at lower concentrations and \textbackslashid, falls at a slower rate for higher thallium concentrations (x 6). The addition of thallium to the Ge-Te network fragments the covalent network and introduces ionic nature to it; the reduction in network connectivity leads to the decrease in switching voltages with thallium content. The decrease in the glass transition temperatures of Ge17Te83-xTlx glasses with increasing thallium concentration supports the idea of decrease in network connectivity with TI addition. The more metallic nature of TI also contributes to the observed reduction in the switching voltages of Ge17Te83-xTlx glasses with TI content. Further, there is an interesting correlation seen between the threshold voltage V-th and the average bond energy, as a function of TI content. In addition, the switching voltages of Ge17Te83-xTlx glasses have been found to decrease with sample thickness almost linearly. The set-reset studies indicate that the Ge17Te83-xTl2 sample can be switched for more than 10 cycles, whereas other glasses could not be reset beyond two switching cycles. (C) 2010 Elsevier B.V. All rights reserved.

Rank dependence of orientational relaxation in dipolar systems

An important yet unsolved problem in the field of orientational relaxation in dipolar liquids is the dependence of the correlation functions C(l)(t), C(l)(t) = [4pi/(2l + 1)SIGMA(m = -l)l [Y(lm)(OMEGA(0)Y(lm)(OMEGA(t))] on the rank l (where Y(lm)(OMEGA) are the usual spherical harmonics). The existing theories on this effect differ in their predictions. To investigate this, we have carried out extensive computer simulations of a Brownian dipolar lattice. The dielectric friction was found to decrease rapidly with increasing l, in qualitative agreement with the predictions of Hubbard-Wolynes. However, the observed effect is much stronger than the predictions of the existing theories.

Systematics of the magnetic-Prandtl-number dependence of homogeneous, isotropic magnetohydrodynamic turbulence

We present the results of our detailed pseudospectral direct numerical simulation (DNS) studies, with up to 1024(3) collocation points, of incompressible, magnetohydrodynamic (MHD) turbulence in three dimensions, without a mean magnetic field. Our study concentrates on the dependence of various statistical properties of both decaying and statistically steady MHD turbulence on the magnetic Prandtl number Pr-M over a large range, namely 0.01 <= Pr-M <= 10. We obtain data for a wide variety of statistical measures, such as probability distribution functions (PDFs) of the moduli of the vorticity and current density, the energy dissipation rates, and velocity and magnetic-field increments, energy and other spectra, velocity and magnetic-field structure functions, which we use to characterize intermittency, isosurfaces of quantities, such as the moduli of the vorticity and current density, and joint PDFs, such as those of fluid and magnetic dissipation rates. Our systematic study uncovers interesting results that have not been noted hitherto. In particular, we find a crossover from a larger intermittency in the magnetic field than in the velocity field, at large Pr-M, to a smaller intermittency in the magnetic field than in the velocity field, at low Pr-M. Furthermore, a comparison of our results for decaying MHD turbulence and its forced, statistically steady analogue suggests that we have strong universality in the sense that, for a fixed value of Pr-M, multiscaling exponent ratios agree, at least within our error bars, for both decaying and statistically steady homogeneous, isotropic MHD turbulence.

Levitation Effect: Role of Symmetry and Dependence of Diffusivity on the Bond Length of Homonuclear and Heteronuclear Diatomic Species

Molecular dynamics investigation of model diatomic species confined to the alpha-cages of zeolite NaY is reported. The dependence of self-diffusivity on the bond length of the diatomic species has been investigated. Three different sets of runs have been carried out. In the first set, the two atoms of the diatomic molecule interact with the zeolite atoms with equal strength (example, O-2, the symmetric case). In the second and third sets which correspond to asymmetric cases, the two atoms of the diatomic molecule interact with unequal strengths (example, CO). The result for the symmetric case exhibits a well-defined maximum in self-diffusivity for an intermediate bond length. In contrast to this, the intermediate asymmetry leads to a less pronounced maximum. For the large asymmetric case, the maximum is completely absent. These findings are analyzed by computing a number of related properties. These results provide a direct confirmation at the microscopic level of the suggestion by Derouane that the supermobility observed experimentally by Kemball has its origin in the mutual cancellation of forces. The maximum in diffusivity from molecular dynamics is seen at the value predicted by the levitation effect. Further, these findings suggest a role for symmetry in the existence of a diffusivity maximum as a function of diameter of the diffusant often referred to as the levitation effect. The nature of the required symmetry for the existence of anomalous diffusivity is interaction symmetry which is different from that normally encountered in crystallography.

Basis set dependence of the molecular electrostatic potential topography. A case study of substituted benzenes

The basis set dependence of the topographical structure of the molecular electrostatic potential (MESP), as well as the effect of substituents on the MESP distribution, has been investigated with substituted benzenes as test cases. The molecules are studied at HF-SCF 3�21G and 6�31G** levels, with a further MESP topographical investigation at the 3�21G, double-zeta, 6�31G*, 6�31G**, double-zeta polarized and triple-zeta polarized levels. The MESP critical points for a 3�21G optimized/6�31G** basis are similar to the corresponding 6�31G** optimized/6�31G** ones. More generally, the qualitative features of the MESP topography computed at the polarized level are independent of the level at which optimization is carried out. For a proper representation of oxygen lone pairs, however, optimization using a polarized basis set is required. The nature of the substituent drastically changes the MESP distribution over the phenyl ring. The values and positions of MESP minima indicate the most active site for electrophilic attack. This point is strengthened by a study of disubstituted benzenes.

Non-Marcus energy gap dependence of electron transfer rate in contact ion pairs. Novel interplay between relaxation and reaction in solution

Electron transfer reactions between donor-acceptor pairs in solution and in organized media exhibit diverse behaviour. Recent experiments have indicated an interesting breakdown of the Marcus parabolic energy gap dependence in the normal regime for back electron transfer from contact ion pairs. A novel explanation of this breakdown has recently been proposed (M. Tachiya and S. Murata, J. Am. Chem. Sec., 116(1994) 2434) which attributes the breakdown to the interplay between the relaxation in the reactant well and the reaction. A particularly interesting aspect of the model is that it envisages the electron transfer in the normal regime to take place from a completely non-equilibrium condition. In this article a time dependent solution of the model is presented for the first time, after generalizing it to include a realistic initial population distribution. The decay of the contact ion pair population is completely non-exponential. This can be used to check the validity of the Tachiya-Murata model. The dynamics of electron transfer from the solvent separated ion pair, which seem to obey the Marcus relation, is exponential.

Dependence of giant magnetoresistance on oxygen stoichiometry and magnetization in polycrystalline La0.67Ba0.33MnOz

We have studied resistivity, magnetization, and magnetoresistance in polycrystalline La0.67Ba0.33MnOz by reducing the oxygen stoichiometry from z=2.99 to 2.80. As the oxygen content decreases, the resistivity of La0.67Ba0.33 MnOz increases and the magnetic transition temperature shifts to lower temperature. A large magnetoresistance effect was observed over a wide temperature range for all samples except the insulating z=2.80 sample. The similarity between our results on oxygen-deficient polycrystalline La0.67 Ba0.33MnOz and films previously reported to have a very large intrinsic magnetoresistance is discussed. At low temperature the magnetoresistance was observed to be strongly dependent on the magnetization. A possible mechanism for this effect is discussed.

Structural dependence of density in high molecular weight esters

The effect of molecular structure on density has been examined in high molecular weight esters (molecular weight 300-900), having varying degrees of branching. Densities were calculated from an empirical equation, which agrees well with the experimental values (error +/-1.5%), irrespective of branching. Since density is related to molecular packing and hence to the molecular rotation, in n-alkanes, the glass transition temperature (T(g)) and density both increase with molecular weight, and hence T(g) is directly related to the density. The esters exhibit a complex behavior. In linear esters the T(g) decreases with molecular weight which is explained from group contribution and molecular interactions. In the +-branched esters, however, T(g) decreases with molecular weight until the molecular weight reaches 600 and increases sharply thereafter. The Y-branched esters show an intermediate behavior. The dependence of T(g) on molecular weight has been explained from the segmental motion.

Reactions of cyanogen radical with alkanes and an explanation for negative temperature dependence of rate constants

Reactions of cyanide radicals with alkanes have been investigated by ab initio methods. It is found that the potential energy surface for reaction of CN with a primary C-H bond in methane has a small positive barrier while reactions of CN with a secondary and a tertiary C-H bond in alkanes are barrierless at the correlated level. A simple explanation for the obtained negative temperature dependence of rate constants for reactions of CN with a secondary and a tertiary C-H bond in alkanes are given in terms of the collision theory of bimolecular reactions. It is shown that for barrierless reactions the negative temperature dependence of the rate constants is attributed to the variation of the pre-exponential factor with temperature.

Large magnetoresistance in La1-xSrxMnO3 and its dependence on magnetization

In this letter we report large magnetoresistance (MR) in ceramic samples of La1?xSrxMnO3 (0.1?x?0.4) in the temperature range 4.2 K?T?350 K in fields up to 6 T. We find that a large negative and isotopic MR exists for the whole composition range studied and the absolute value of resistivity change on application of magnetic field is more for samples with lower x which have higher resistivity. We find that the large MR occurs in the ferromagnetic state only and MR has a close relation with the magnetization M. © 1995 American Institute of Physics.

Electronic conduction in LaNiO3-delta: the dependence on the oxygen stoichiometry delta

We report a systematic study of the electronic transport properties of the metallic perovskite oxide LaNiO3-delta as a function of the oxygen stoichiometry delta (delta less than or equal to 0.14). The electrical resistivity, magnetoresistance, susceptibility, Hall effect and thermopower have been studied, All of the transport coefficients are dependent on the value of delta. The resistivity increases almost exponentially as delta increases. We relate this increase in rho to the creation of Ni2+ with square-planar coordination. We find that there is a distinct T-1.5-contribution to the resistivity over the whole temperature range. The thermopower is negative, as expected for systems with electrons as the carrier, but the Hall coefficient is positive. We have given a qualitative and quantitative explanation for the different quantities observed and their systematic variation with the stoichiometry delta.

Levitation effect and its dependence on sorbate concentration

Earlier work has reported the existence of a diffusion anomaly in porous solids at dilute sorbate concentrations. In this work we have carried out molecular dynamics simulations at higher sorbate concetrations. Results indicate the persistence of a diffusion anomaly even at significantly higher sorbate concentrations, which means that this anomaly can be used for separation of mixtures under conditions prevailing in industries.