Orbital angular momentum exchange in the interaction of twisted light with molecules

In the interaction of molecules with light endowed with orbital angular momentum, an exchange of orbital angular momentum in an electric dipole transition occurs only between the light and the center of mass motion; i.e., internal "electronic-type" motion does not participate in any exchange of orbital angular momentum in a dipole transition. A quadrupole transition is the lowest electric multipolar process in which an exchange of orbital angular momentum can occur between the light, the internal motion, and the center of mass motion. This rules out experiments seeking to observe exchange of orbital angular momentum between light beams and the internal motion in electric dipole transitions.     

Stacked lattice boxes

We study the number of solutions of the Diophantine equationn=x ₁ x ₂+x ₂ x ₃+x ₃ x ₄+...+x _k x _k+1 The combinatorial interpretation of this equation provides the name stacked lattices boxes. The study of these objects unites three separate threads in number theory: (1) the Liouville methods, (2) MacMahon's partitions withk different parts, (3) the asymptotics of divisor sums begun by Ingham.Partially supported by National Science Foundation Grant DMS-9206993, USA.     

Inter-particle interaction induced by broadband radiation

The recent fabrication of optical traps using super-continuum light impresses the need for a theory of inter-particle interactions under such conditions. Development of the theory provides a basis for calculation of the observations expected under experimental conditions. An expression for the inter-particle potential energy induced by continuum states of light is first derived using quantum electrodynamics. This energy expression is cast as a function of the spectral irradiance of the light, and the electric susceptibility of the interacting particles. Specific results are derived for light with a Lorentzian spectrum. It is shown that by filtering part of the spectrum, it is possible to exert control over the length of linear particle chains organized along the Poynting vector. The results exhibit scope for the optical fabrication of moldable structures using broadband light.     

Infrared spectrum of the novel electron-deficient BH(4) radical in solid neon

Laser-ablated boron reacts with hydrogen on condensation in excess neon to give BH4 radical, BH4- anion, and B2H6 as the major products. Identifications are based on 10B and D substitution, DFT frequency calculations, and comparison to previous spectra. Infrared spectra of BH4 support the C2v structure deduced from previous ESR spectra and theoretical calculations with two normal B-H bonds and two long B-H bonds for this novel electron-deficient radical. NBO analysis suggests that the two long B-H bonds and the H- -H bond are one-electron bonds.     

Argon matrix absorption spectra of ClO, BrO, and IO and emission spectra of IO

Absorption spectra of ClO, BrO, and IO and the emission spectrum of IO have been observed from argon matrix samples prepared by microwave discharging the reagent mixture before condensation. Vibronic progressions were observed for each system. The spectroscopic scopic constants T_e, ω′_e, ω_ex′_e, ω″_e, and ω_ex″_e were evaluated from the absorption and emission data for comparison with gas-phase constants. Very good agreement is found for ClO. The argon matrix observations dictate a revision of the gas-phase vibronic assignments for BrO. The ground-state vibrational fundamental and T_e for argon matrix isolated IO are similar to the gas-phase values, but a lower excited-state spacing is found in the matrix.     

Automated parallel, multi-step polymer-assisted solution phase (PASP) synthesis of substituted benzimidazole derivatives

The automated polymer-assisted solution phase (PASP) synthesis of a 72 member library of 2-alkylthio-benzimidazoles 16 and benzimidazolin-2-ones 17 using commercially available robotic workstations is described. By incorporating both automated aqueous work-ups, in-line scavenging and 'catch and release' protocols the desired compounds were obtained directly in good yields and excellent purities without the need for conventional chromatographic purification. The synthesis described demonstrates how both manual and automated equipment may be utilised together to provide a versatile approach that facilitates parallel compound synthesis.     

Matrix infrared spectroscopic study of magnesium carbene and carbenoid radicals and analysis of their bonding with density functional calculations

Magnesium atoms generated by laser ablation were reacted with methyl halides and methane diluted in argon. Among the reaction products were the metal carbene species, MgCH2, and carbenoid radicals, XMgCH2 (where X = H, F, Cl, and Br). This investigation reports matrix infrared spectra for Mg carbene and carbenoid species in a cold matrix, and electronic structure calculations for these and related beryllium species. An unusual bonding interaction for the MCH2 species is described in which the bonding in the alpha and beta manifolds is qualitatively different. Vibrational frequencies and analysis of the results of density functional calculations provide information about the nature of the bonding in these species and allow for a comparison to the well-known transition metal Fischer- and Schrock-type carbene complexes. The special difficulties of computational modeling of vibrations in highly polar molecules are discussed.