Trends in C-O and C-N bond formations over transition metal surfaces: An insight into kinetic sensitivity in catalytic reactions

Transition metal catalyzed bond formation is a fundamental process in catalysis and is of general interest throughout chemistry. To date, however, the knowledge of association reactions is rather limited, relative to what is known about dissociative processes. For example, surprisingly little is known about how the bond-forming ability of a metal, in general, varies across the Periodic Table. In particular, the effect of reactant valency on such trends is poorly understood. Herein, the authors examine these key issues by using density functional theory calculations to study CO and CN formations over the 4d metals. The calculations reveal that the chemistries differ in a fundamental way. In the case of CO formation, the reaction enthalpies span a much greater range than those of CN formation. Moreover, CO formation is found to be kinetically sensitive to the metal; here the reaction barriers (E-a) are found to be influenced by the reaction enthalpy. CN formation, conversely, is found to be relatively kinetically insensitive to the metal, and there is no correlation found between the reaction barriers and the reaction enthalpy. Analysis has shown that at the final adsorbed state, the interaction between N and the surface is relatively greater than that of O. Furthermore, in comparison with O, relatively less bonding between the surface and N is observed to be lost during transition state formation. These greater interactions between N and the surface, which can be related to the larger valency of N, are found to be responsible for the relatively smaller enthalpy range and limited variation in E-a for CN formation. (C) 2007 American Institute of Physics.

Effect of quantization of vibrations on the structural properties of crystals

We study the structural effects produced by the quantization of vibrational degrees of freedom in periodic crystals at zero temperature. To this end we introduce a methodology based on mapping a suitable subspace of the vibrational manifold and solving the Schrödinger equation in it. A number of increasingly accurate approximations ranging from the quasiharmonic approximation (QHA) to the vibrational self-consistent field (VSCF) method and the exact solution are described. A thorough analysis of the approximations is presented for model monatomic and hydrogen-bonded chains, and results are presented for a linear H-F chain where the potential-energy surface is obtained via first-principles electronic structure calculations. We focus on quantum nuclear effects on the lattice constant and show that the VSCF is an excellent approximation, meaning that correlation between modes is not extremely important. The QHA is excellent for covalently bonded mildly anharmonic systems, but it fails for hydrogen-bonded ones. In the latter, the zero-point energy exhibits a nonanalytic behavior at the lattice constant where the H atoms center, which leads to a spurious secondary minimum in the quantum-corrected energy curve. An inexpensive anharmonic approximation of noninteracting modes appears to produce rather good results for hydrogen-bonded chains for small system sizes. However, it converges to the incorrect QHA results for increasing size. Isotope effects are studied for the first-principles H-F chain. We show how the lattice constant and the H-F distance increase with decreasing mass and how the QHA proves to be insufficient to reproduce this behavior.

Polarization and Angular Correlation Studies of X-Rays Emitted in Relativistic Ion-Atom Collisions

Particle and photon polarization phenomena occurring in collisions of relativistic ions with matter have recently attracted particular interest. Investiga- tions of the emitted characteristic x-ray and radiative electron capture radiation has been found to be a versatile tool for probing our present understanding of the dynamics of particles in extreme electromagnetic ¯elds. Owing to the progress in x-ray detector technology, in addition, accurate measurements of the linear po- larization for hard x-ray photons as well as the determination of the polarization plane became possible. This new diagnostic tool enables one today to derive in- formation about the polarization of the ion beams from the photon polarization features of the radiative electron capture process.

Periodic FDTD analysis of a 2-D leaky-wave planar antenna based on dipole frequency selective surfaces

A periodic finite-difference time-domain (FDTD) analysis is presented and applied for the first time in the study of a two-dimensional (2-D) leaky-wave planar antenna based on dipole frequency selective surfaces (FSSs). First, the effect of certain aspects of the FDTD modeling in the modal analysis of complex waves is studied in detail. Then, the FDTD model is used for the dispersion analysis of the antenna of interest. The calculated values of the leaky-wave attenuation constants suggest that, for an antenna of this type and moderate length, a significant amount of power reaches the edges of the antenna, and thus diffraction can play an important role. To test the validity of our dispersion analysis, measured radiation patterns of a fabricated prototype are presented and compared with those predicted by a leaky-wave approach based on the periodic FDTD results.

Efficient analysis, design, and filter applications of EBG waveguide with periodic resonant loads

An efficient analysis and design of an electromagnetic-bandgap (EBG) waveguide with resonant loads is presented. Equivalent-circuit analysis is employed to demonstrate the differences between EBG waveguides with resonant and nonresonant loadings. As a result of the resonance, transmission zeros at finite frequencies emerge. The concept is demonstrated in E-plane waveguides. A generic fast and efficient formulation is presented, which starts from the generalized scattering matrix of the unit cell and derives the dispersion properties of the infinite structure. Both real and imaginary parts of the propagation constant are derived and discussed. The Floquet wavelength and impedance are also presented. The theoretical results are validated by comparison with simulations of a finite structure and experimental results. The application of the proposed EBG waveguide in the suppression of the spurious passband of a conventional E-plane filter is presented by experiment.

Tailoring the AMC and EBG characteristics of periodic metallic arrays printed on grounded dielectric substrate

The artificial magnetic conductor (AMC) and electromagnetic band gap (EBG) characteristics of planar periodic metallic arrays printed on grounded dielectric substrate are investigated. The currents induced on the arrays are presented for the first time and their study reveals two distinct resonance phenomena associated with these surfaces. A new technique is presented to tailor the spectral position of the AMC operation and the EBG. Square patch arrays with fixed element size and variable periodicities are employed as working examples to demonstrate the dependence of the spectral AMC and EBG characteristics on array parameters. It is revealed that as the array periodicity is increased, the AMC frequency is increased, while the EBG frequency is reduced. This is shown to occur due to the different nature of the resonance phenomena and the associated underlying physical mechanisms that produce the two effects. The effect of substrate thickness is also investigated. Full wave method of moments (MoM) has been employed for the derivation of the reflection characteristics, the currents and the dispersion relations. A uniplanar array with simultaneous AMC and EBG operation is demonstrated theoretically and experimentally.

Development of a QSPR correlation for the parachor of 1,3-dialkyl imidazolium based ionic liquids

Ionic liquids have received significant interest from both academia and industry for a wide range of applications which often requires knowledge of their thermophysical properties. Quantitative structure-property relationship correlations and group contribution methods for thermophysical properties of ionic liquids are a basic necessity for the development of computer aided molecular design approaches for these liquids and subsequently offer the potential for designing an ionic liquid having a desirable set of thermophysical properties. However, the limited availability of experimental thermophysical data and their quality have prevented the development of such tools. Based on previously reported experimental surface tension data, a correlation of the parachors with the molar volume of the ionic liquids has been developed. The predicted parachor values have been shown to be in good agreement with the experimental data. A maximum deviation of

Convergence acceleration of the doubly periodic Green's function for the analysis of thin wire arrays

A method is proposed to accelerate the evaluation of the Green's function of an infinite double periodic array of thin wire antennas. The method is based on the expansion of the Green's function into series corresponding to the propagating and evanescent waves and the use of Poisson and Kummer transformations enhanced with the analytic summation of the slowly convergent asymptotic terms. Unlike existing techniques the procedure reported here provides uniform convergence regardless of the geometrical parameters of the problem or plane wave excitation wavelength. In addition, it is numerically stable and does not require numerical integration or internal tuning parameters, since all necessary series are directly calculated in terms of analytical functions. This means that for nonlinear problem scenarios that the algorithm can be deployed without run time intervention or recursive adjustment within a harmonic balance engine. Numerical examples are provided to illustrate the efficiency and accuracy of the developed approach as compared with the Ewald method for which these classes of problems requires run time splitting parameter adaptation.