Mechanisms of Auger-induced chemistry derived from wave packet dynamics

To understand how core ionization and subsequent Auger decay lead to bond breaking in large systems, we simulate the wave packet dynamics of electrons in the hydrogenated diamond nanoparticle C_(197)H_(112). We find that surface core ionizations cause emission of carbon fragments and protons through a direct Auger mechanism, whereas deeper core ionizations cause hydrides to be emitted from the surface via remote heating, consistent with results from photon-stimulated desorption experiments [Hoffman A, Laikhtman A, (2006) J Phys Condens Mater 18:S1517–S1546]. This demonstrates that it is feasible to study the chemistry of highly excited large-scale systems using simulation and analysis tools comparable in simplicity to those used for classical molecular dynamics

Product Protection, the Key to Developing High Performance Methane Selective Oxidation Catalysts

Selective, direct conversion of methane to methanol might seem an impossible task since the C−H bond energy of methane is 105 kcal mol^(−1) compared to the C−H bond energy for methanol of 94. We show here that the Catalytica catalyst is successful because the methanol is protected as methyl bisulfate, which is substantially less reactive than methanol toward the catalyst. This analysis suggests a limiting performance for systems that operate by this type of protection that is well above the Catalytica system

Foliation of the Kottler-Schwarzschild-De Sitter Spacetime by Flat Spacelike Hypersurfaces

There exist Kruskal like coordinates for the Reissner-Nordstrom (RN) black hole spacetime which are regular at coordinate singularities. Non existence of such coordinates for the extreme RN black hole spacetime has already been shown. Also the Carter coordinates available for the extreme case are not manifestly regular at the coordinate singularity, therefore, a numerical procedure was developed to obtain free fall geodesics and flat foliation for the extreme RN black hole spacetime. The Kottler-Schwarzschild-de Sitter (KSSdS) spacetime geometry is similar to the RN geometry in the sense that, like the RN case, there exist non-singular coordinates when there are two distinct coordinate singularities. There are no manifestly regular coordinates for the extreme KSSdS case. In this paper foliation of all the cases of the KSSdS spacetime by flat spacelike hypersurfaces is obtained by introducing a non-singular time coordinate.Comment: 12 pages, 4 figure

Non Abelian Sugawara Construction and the q-deformed N=2 Superconformal Algebra

The construction of a q-deformed N=2 superconformal algebra is proposed in terms of level 1 currents of ${\cal{U}}_{q} ({\widehat{su}}(2))$ quantum affine Lie algebra and a single real Fermi field. In particular, it suggests the expression for the q-deformed Energy-Momentum tensor in the Sugawara form. Its constituents generate two isomorphic quadratic algebraic structures. The generalization to ${\cal{U}}_{q} ({\widehat{su}}(N+1))$ is also proposed.Comment: AMSLATEX, 21page

Theoretical studies of Si and GaAs surfaces and initial steps in the oxidation

Using ab initio quantum chemical methods (generalized valence bond), we examine (i) the electronic states of Si (111) and GaAs (110) surface, (ii) the relaxation of the Si (111) surface, (iii) the reconstruction of the GaAs surface, (iv) the initial steps in the chemisorption of O_2 on Si (111), and (v) the bonding of O atom to Ga and As centers

Angle Dependent Magnetoresistance of the Layered Organic Superconductor \kappa-(ET)2Cu(NCS)2: Simulation and Experiment

The angle-dependences of the magnetoresistance of two different isotopic substitutions (deuterated and undeuterated) of the layered organic superconductor \kappa-(ET)2Cu(NCS)2 are presented. The angle dependent magnetoresistance oscillations (AMRO) arising from the quasi-one-dimensional (Q1D) and quasi-two-dimensional (Q2D) Fermi surfaces in this material are often confused. By using the Boltzman transport equation extensive simulations of the AMRO are made that reveal the subtle differences between the different species of oscillation. No significant differences are observed in the electronic parameters derived from quantum oscillations and AMRO for the two isotopic substitutions. The interlayer transfer integrals are determined for both isotopic substitutions and a slight difference is observed which may account for the negative isotope effect previously reported [1]. The success of the semi-classical simulations suggests that non-Fermi liquid effects are not required to explain the interlayer-transport in this system.Comment: 15 pages, 16 figure

Multiparadigm modeling of dynamical crack propagation in silicon using a reactive force field

We report a study of dynamic cracking in a silicon single crystal in which the ReaxFF reactive force field is used for several thousand atoms near the crack tip, while more than 100 000 atoms are described with a nonreactive force field. ReaxFF is completely derived from quantum mechanical calculations of simple silicon systems without any empirical parameters. Our results reproduce experimental observations of fracture in silicon including changes in crack dynamics for different crack orientations

Iridium complexes bearing a PNP ligand, favoring facile C(sp^3)–H bond cleavage

Hydrogen iodide is lost upon reaction of PNP with IrI_3, where PNP = 2,6-bis-(di-t-butylphosphinomethyl)pyridine to give crystallographically characterized Ir(PNP)*(I)_2, which reacts with H_2 to give Ir(PNP)(H)(I)_2. Ir(PNP)(Cl)_3 is relatively inert towards the intramolecular C–H activation of the tert-butyl's of the PNP ligand