Non-Born-Oppenheimer approximation for very weakly bound states of molecular anions

The influence of nuclear rotation on weak electron binding in the long range field of a linear polar molecule is treated in a way that leads ultimately, with suitable approximation, to the familiar equations for close coupling of electron-nuclear-rotational motions. Subsequently, a conventional pseudopotential approximation is invoked to examine the rotational spectra of HCN and DCN anions. It is shown that the number of rotationally excited anion states cannot be reliably predicted by assuming that zero binding occurs when the rotational energy equals the electron affinity obtained in the Born-Oppenheimer approximation. A method is suggested for combining accurate molecular orbital and parameterized pseudopotential methods to provide accurate electron affinities for very weakly bound anionic states.     

Synthesis and characterization of oxide cathode materials of the system (1-x-y)LiNiO<Subscript>2</Subscript>·xLi<Subscript>2</Subscript>MnO<Subscript>3</Subscript>·yLiCoO<Subscript>2</Subscript>

Composite cathode materials produced by integrating isostructural (2D-layered) compounds LiNiO₂, LiCoO₂, and Li₂MnO₃ (Li(Li_1/3Mn_2/3)O₂) have been investigated utilizing a compositional phase diagram. The samples were characterized by multiple techniques to establish structure–property relationships. Specifically, for structural characterization, powder X-ray diffraction, scanning electron microscopy, thermo-gravimetric analysis, and X-ray photoelectron spectroscopy were carried out. For properties, electrochemical characterization was carried out. The best composition showed a discharge capacity of 244 mAh/g (C/15 rate) in the testing range of 4.6–2 V, with good coulombic efficiency and cyclability.     

Uniform directional alignment of single-walled carbon nanotubes in viscous polymer flow

In this work, we probed the effects of shear flow on the alignment of dispersed single-walled carbon nanotubes in polymer solutions. Two different systems were compared: Single-walled carbon nanotubes dispersed using an anionic surfactant and single-walled carbon nanotubes dispersed using an anionic surfactant and a weakly binding polymer. It was determined that the addition of the weakly binding polymer increased the degree of dispersion of the carbon nanotubes and the ability to induce their alignment when subjected to shear forces.     

Sensitivity analysis of thermodynamic properties of liquid water: a general approach to improve empirical potentials

A sensitivity analysis of bulk water thermodynamics is presented in an effort to understand the relation between qualitative features of molecular potentials and properties that they predict. The analysis is incorporated in molecular dynamics simulations and investigates the sensitivity of the Helmholtz free energy, internal energy, entropy, heat capacity, pressure, thermal pressure coefficient, and static dielectric constant to components of the potential rather than the parameters of a given functional form. The sensitivities of the properties are calculated with respect to the van der Waals repulsive and the attractive parts, plus short- and long-range Coulomb parts of three four site empirical water potentials: TIP4P, Dang-Chang and TTM2R. The polarization sensitivity is calculated for the polarizable Dang-Chang and TTM2R potentials. This new type of analysis allows direct comparisons of the sensitivities for different potentials that use different functional forms. The analysis indicates that all investigated properties are most sensitive to the van der Waals repulsive, the short-range Coulomb and the polarization components of the potentials. When polarization is included in the potentials, the magnitude of the sensitivity of the Helmholtz free energy, internal energy, and entropy with respect to this part of the potential is comparable in magnitude to the other electrostatic components. In addition similarities in trends of observed sensitivities for nonpolarizable and polarizable potentials lead to the conclusion that the complexity of the model is not of critical importance for the calculation of these thermodynamic properties for bulk water. The van der Waals attractive and the long-range Coulomb sensitivities are relatively small for the entropy, heat capacity, thermal pressure coefficient and the static dielectric constant, while small changes in any of the potential contributions will significantly affect the pressure. The analysis suggests a procedure for modification of the potentials to improve predictions of thermodynamic properties and we demonstrate this general approach for modifying potentials for one of the potentials.     

Dynamics of alkyl ammonium intercalants within organically modified montmorillonite: Dielectric relaxation and ionic conductivity

The low-frequency (0.01 Hz-10 MHz) dynamic characteristics of alkyl quaternary ammonium exchanged montmorillonite (SC20A) were investigated to determine the correlation between temperature-dependent changes in the interlayer structure and collective mobility of the surfactant. From 25 to 165 degrees C, SC20A exhibits two interlayer transitions, one ascribed to the melting of the intercalated alkyl chains of the surfactant (20-40 degrees C) and another associated with an abrupt decrease in the interlayer's coefficient of thermal expansion (100 degrees C). For this temperature range, the excess surfactant and residual electrolytes present in commercially manufactured SC20A enhance the direct current conductivity and increase low-frequency space-charge polarization, which is believed to occur across percolation paths established by the surfaces of the SC20A crystallites. In contrast, a higher-frequency relaxation, which was less sensitive to process history and impurity content, is ascribed to relaxation within the interlayer at the surfactant-aluminosilicate interface electrostatic couple. The temperature dependence of these dielectric relaxations indicated a drastic increase in mobility as the interlayer organic phase transitions from static and glasslike into molten and mobile. Overall, SC20A displayed features of alternating current universality, including time-temperature superposition, common in other types of disordered ion-conducting media. The presence of long-range transport and its sensitivity to low amounts of impurities imply that from a dynamic perspective the local environment of the surfactants are substantially diverse and a minority fraction, such as at the edge of the crystallite (gallery and aluminosilicate layer), may dominate the lower-frequency dielectric response.     

Experimental demonstration of self-collimation inside a three-dimensional photonic crystal

We present our experimental demonstration of self-collimation inside a three-dimensional (3D) simple cubic photonic crystal at microwave frequencies. The photonic crystal was designed with unique dispersion property and fabricated by a high precision computer-controlled machine. The self-collimation modes were excited by a grounded waveguide feeding and detected by a scanning monopole. Self-collimation of electromagnetic waves in the 3D photonic crystal was demonstrated by measuring the 3D field distribution, which was shown as a narrow collimated beam inside the 3D photonic crystal but a diverged beam in the absence of the photonic crystal.     

Multivariate logistic regression with incomplete covariate and auxiliary information

In this article, we propose and explore a multivariate logistic regression model for analyzing multiple binary outcomes with incomplete covariate data where auxiliary information is available. The auxiliary data are extraneous to the regression model of interest but predictive of the covariate with missing data. Horton and Laird [N.J. Horton, N.M. Laird, Maximum likelihood analysis of logistic regression models with incomplete covariate data and auxiliary information, Biometrics 57 (2001) 34–42] describe how the auxiliary information can be incorporated into a regression model for a single binary outcome with missing covariates, and hence the efficiency of the regression estimators can be improved. We consider extending the method of [9] to the case of a multivariate logistic regression model for multiple correlated outcomes, and with missing covariates and completely observed auxiliary information. We demonstrate that in the case of moderate to strong associations among the multiple outcomes, one can achieve considerable gains in efficiency from estimators in a multivariate model as compared to the marginal estimators of the same parameters.     

Ice nucleation and phase behavior on oligo(ethylene glycol) and hydroxyl self-assembled monolayers: simulations and experiments

The nucleation and phase behavior of ultrathin D2O-ice overlayers have been studied on oligo(ethylene glycol) (OEG)-terminated and hydroxyl self-assembled monolayers (SAMs) at low temperatures in ultrahigh vacuum. Infrared reflection-absorption spectroscopy (IRAS) is used to characterize the ice overlayers, the SAMs, and the interactions occurring between the ice and the SAM surfaces. Spectral simulations, based on optical models in conjunction with Maxwell Garnett effective medium theory, point out the importance of including voids in the modeling of the ice structures, with void fractions reaching 60% in some overlayers. The kinetics of the phase transition from amorphous-like to crystalline-like ice upon isothermal annealing at 140 K is found to depend on the conformational state of the supporting OEG SAM surface. The rate is fast on the helical OEG SAMs and slow on the corresponding all-trans SAMs. This difference in kinetics is most likely due to a pronounced D2O interpenetration and binding to the all-trans segments of the ethylene glycol portion of the SAM. No such penetration and binding was observed on the helical OEG SAM.     

The notion of computation is fundamental to an autonomous neuroscience

The increasing sophistication of the tools and results of cellular and molecular neuroscience would appear to suggest that explanatory force in neuroscience is defined by reduction to molecular biology. This view, however, is mistaken in that it loses sight of the goal of neuroscience proper: the characterization of the information content of biophysical variables and the transformation of these variables that lead to behaviors. Neuroscience is thus distinguished from applied molecular and cellular biology by the notion of computation. In this commentary, I will show how the notion of computation in neuroscience differs from that of other fields that investigate complex systems and argue that computation at various levels of neural organization is the paramount goal of neuroscientific explanation and not the so‐called reduction of “mind to molecules.” © 2009 Wiley Periodicals, Inc. Complexity, 16,10–19, 2010     

Muon spin relaxation in heavy fermion systems

Heavy fermion systems have received a great deal of study by a wide variety of techniques, includingSR. In a number of systems, coexisting superconducting and magnetic states have been reported, leading to speculation of an intimate connection between magnetism and superconductivity in these compounds. We observe a spontaneous magnetic field in the superconducting phase of UPt₃. In addition, the broadening of the transverse field muon precession signal only onsets approximately 60 mK below the superconductingT _c. Our results provide evidence that the lower superconducting phase in theH-T phase diagram of UPt₃ is characterised by broken time-reversal symmetry. Measurements of URu₂Si₂ and CeCu_2.2Si₂ indicate that the magnetically ordered volume fraction is temperature dependent in both systems.