Uv Multiphoton Induced Chemistry of Nitrobenzene in Solution

The technique of Multiphoton Induced Chemistry (MPIC) has been employed to initiate ion-molecule chemistry of organic molecules in solution. We report one of the first examples of the use of liquid phase multiphoton ionization (MPI) to prepare organic cations, which then react with the solvent in ionmolecule processes. The products obtained in this chemical sequence are significantly different from those observed in conventional or multiphoton-induced neutral chemistry in the same solvent. The particular example explored in this work is the reactivity of the nitrobenzene cation in methanol solvent. Products of the ion-molecule chemistry, detected by gas chromatography/mass spectrometry, are phenol and benzyl alcohol. These products depend upon the square of the laser intensity. It is shown by ionization current measurements in a conductance cell, that ionic species are produced as precursors to the observed products. The implications of this application of MPI are briefly discussed. A preliminary report on the unimolecular chemistry of the highly excited neutral molecule is also included. The product of this channel is nitrosobenzene. It is shown, in this case, that the reactive state is most likely a highly vibrationally excited ground state molecule, not the lowest triplet level invoked in conventional photochemistry

Modeling the Pinning of Au and Ni Clusters on Graphite

The pinning of size-selected AuN and NiN clusters on graphite, for N=7–100, is investigated by means of molecular dynamics simulations and the results are compared to experiment and previous work with Ag clusters. Ab initio calculations of the binding of the metal adatom and dimers on a graphite surface are used to parametrize the potentials used in the simulations. The clusters are projected normally towards a graphite surface and the value of the energy at which pinning first occurs, EP, is determined. Pinning is shown to occur when a surface defect, made by the cluster interaction, is first produced. The simulations give a good agreement with the experimentally determined pinning energy thresholds and the heights of the clusters on the surface. The gold clusters are shown to be flatter and more spread out than the nickel clusters which are more compact

Gold Adatoms and Dimers on Relaxed Graphite Surfaces

The interaction of deposited gold adatoms and dimers with multilayer relaxed graphite surfaces is investigated through a density functional approach with numerical orbitals and a relativistic core pseudopotential. The energy landscape for a gold adatom along [110] agrees with scanning tunneling microscopy observations including the preferred β binding site for adatoms and the mobility difference between silver and gold adatoms. Deposited particles are shown to induce surface deformation and polarization. Static relaxation and dynamic simulations indicate that the energetically preferred binding orientation for a gold dimer is normal rather than parallel to the graphite surface. The dimer response to a simulated scanning tunneling microscopy tip is investigated by molecular dynamics simulations

Vapor Deposited Cr-doped ZnS Thin Films: Towards Optically Pumped Mid-Infrared Waveguide Lasers

Compact, affordable mid-IR lasers require the development of gain materials in waveguide form. We report on the high vacuum deposition of Cr:ZnS films with concentration ranging from 1018-1020 dopants/cm3 . At low concentrations, films display well-isolated absorption associated with substitutional Cr2+ ions in the lattice. Spatial modulation of the dopant concentration suppresses the absorption associated with this substitution. Lateral crystallite sizes less than 30 nm are associated with the lowest substrate temperatures (\u3c50 °C) used during deposition, and waveguide losses as low as 8dB/cm are observed. These materials are promising candidates as gain media for fabrication of waveguide mid-IR lasers

Nanomaterials in Sensors

This Special Issue of Nanomaterials is focused on the continuing implementation of nanomaterials and nanostructures in the development of more sensitive and more specific sensing devices. As a result, these new devices employ smaller sensing elements and provide more “real time” capability. Often, the inclusion of nanomaterials leads to sensing elements for targets that were previously inaccessible

The bell that rings light: a primer in quantum mechanics and chemical bonding

This book is an introduction to quantum mechanics and mathematics that leads to the solution of the Schrodinger equation. It can be read and understood by undergraduates without sacrificing the mathematical details necessary for a complete solution giving the shapes of molecular orbitals seen in every chemistry text. Readers are introduced to many mathematical topics new to the undergraduate curriculum, such as basic representation theory, Schur's lemma, and the Legendre polynomials