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.

Importance of electronegativity differences and surface structure in molecular dissociation reactions at transition metal surfaces

The dissociative adsorption of N-2 has been studied at both monatomic steps and flat regions on the surfaces of the 4d transition metals from Zr to Pd. Using density functional theory (DFT) calculations, we have determined and analyzed the trends in both straight reactivity and structure sensitivity across the periodic table. With regards to reactivity, we find that the trend in activation energy (Ea) is determined mainly by a charge transfer from the surface metal atoms to the N atoms during transition state formation, namely, the degree of ionicity of the N-surface bond at the transition state. Indeed, we find that the strength of the metal-N bond at the transition state (and therefore the trend in Ea) can be predicted by the difference in Mulliken electronegativity between the metal and N. Structure sensitivity is analyzed in terms of geometric and electronic effects. We find that the lowering of Ea due to steps is more pronounced on the right-hand side of the periodic table. It is found that for the early transition metals the geometric and electronic effects work in opposition when going from terrace to step active site. In the case of the late 4d metals, however, these effects work in combination, producing a more marked reduction in Ea.

Ultracold fluorine production via Doppler cooled BeF

Large parts of the periodic table cannot be cooled by current laser-based methods. We investigate whether zero energy fragmentation of laser cooled fluorides is a potential source of ultracold fluorine atoms. We report new ab initio calculations on the lowest electronic states of the BeF diatomic molecule including spin-orbit coupling, the calculated minima for the valence electronic states being within 1 pm of the spectroscopic values. A four colour cooling scheme based on the A2? ? X2S+ transition is shown to be feasible for this molecule. Multi-Reference Configuration Interaction (MRCI) potentials of the lowest energy Rydberg states are reported for the first time and found to be in good agreement with experimental data. A series of multi-pulse excitation schemes from a single rovibrational level of the cooled molecule are proposed to produce cold fluorine atoms.

Enhanced transmission in microwave arrays of periodic sub-wavelength apertures

In this paper we have conclusively proven that the "enhanced" optical transmission through a periodic array of sub-wavelength holes in metal films (Ebbessen's experiment) is the result of the array periodicity. This work has overturned the commonly accepted theory that the surface plasmons were responsible for the transmission enhancement. It was demonstrated that the reflectance, transmittance and frequency selectivity of the multilayered arrays can be efficiently modified by the aperture shapes.

The periodic variations of a white-light flare observed with ULTRACAM

High time resolution observations of a white-light flare on the active star EQ PegB show evidence of intensity variations with a period of ≈10 s. The period drifts to longer values during the decay phase of the flare. If the oscillation is interpreted as an impulsively-excited, standing-acoustic wave in a flare loop, the period implies a loop length of ≈3.4 Mm and ≈6.8 Mm for the case of the fundamental mode and the second harmonic, respectively. However, the small loop lengths imply a very high modulation depth making the acoustic interpretation unlikely. A more realistic interpretation may be that of a fast-MHD wave, with the modulation of the emission being due to the magnetic field. Alternatively, the variations could be due to a series of reconnection events. The periodic signature may then arise as a result of the lateral separation of individual flare loops or current sheets with oscillatory dynamics (i.e., periodic reconnection).

Hydrogen bonding and collective proton modes in clusters and periodic layers of squaric acid: A density functional study

Hydrogen bonding in clusters and extended layers of squaric acid molecules has been investigated by density functional computations. Equilibrium geometries, harmonic vibrational frequencies, and energy barriers for proton transfer along hydrogen bonds have been determined using the Car-Parrinello method. The results provide crucial parameters for a first principles modeling of the potential energy surface, and highlight the role of collective modes in the low-energy proton dynamics. The importance of quantum effects in condensed squaric acid systems has been investigated, and shown to be negligible for the lowest-energy collective proton modes. This information provides a quantitative basis for improved atomistic models of the order-disorder and displacive transitions undergone by squaric acid crystals as a function of temperature and pressure. (C) 2001 American Institute of Physics.

Near-field distribution of optical transmission of periodic subwavelength holes in a metal film

Optical transmission of a two-dimensional array of subwavelength holes in a metal film has been numerically studied using a differential method. Transmission spectra have been calculated showing a significant increase of the transmission in certain spectral ranges corresponding to the excitation of the surface polariton Bloch waves on a metal surface with a periodic hole structure. Under the enhanced transmission conditions, the near-field distribution of the transmitted light reveals an intensity enhancement greater than 2 orders of magnitude in localized (similar to 40 nm) spots resulting from the interference of the surface polaritons Bragg scattered by the holes in an array.

Optimal basis set for electronic structure calculations in periodic systems

An efficient method for calculating the electronic structure of systems that need a very fine sampling of the Brillouin zone is presented. The method is based on the variational optimization of a single (i.e., common to all points in the Brillouin zone) basis set for the expansion of the electronic orbitals. Considerations from k.p-approximation theory help to understand the efficiency of the method. The accuracy and the convergence properties of the method as a function of the optimal basis set size are analyzed for a test calculation on a 16-atom Na supercell.

Luminous blue variables as the progenitors of supernovae with quasi-periodic radio modulations

The interaction between supernova ejecta and circumstellar matter, arising from previous episodes of mass loss, provides us with a means of constraining the progenitors of supernovae. Radio observations of a number of supernovae show quasi-periodic deviations from a strict power-law decline at late times. Although several possibilities have been put forward to explain these modulations, no single explanation has proven to be entirely satisfactory. Here we suggest that Luminous blue variables undergoing S-Doradus type variations give rise to enhanced phases of mass loss that are imprinted on the immediate environment of the exploding star as a series of density enhancements. The variations in mass loss arise from changes in the ionization balance of Fe, the dominant ion that drives the wind. With this idea, we find that both the recurrence timescale of the variability and the amplitude of the modulations are in line with the observations. Our scenario thus provides a natural, single-star explanation for the observed behaviour that is, in fact, expected on theoretical grounds.