Reflection absorption infrared study of the adsorption of dimethylamine on copper (1 1 0) and nickel (1 1 1) surfaces

The adsorption of dimethylamine on Cu(1 1 0) and Ni(1 1 1) has been studied by reflection absorption infrared spectroscopy. For Cu(1 1 0), adsorption was molecular at 80 and 300 K and for submonolayer dimethylamine the appearance of A′ and not A″ modes indicated C_s symmetry. Similar bonding was found for Ni(1 1 1) at 170 K. Annealing the adlayer to 350 K resulted in the formation of a new species on Ni(1 1 1), similar to that which has been identified as methylaminocarbyne on Pt(1 1 1). In contrast only molecular dimethylamine was identified on Cu(1 1 0), with H-bonded interactions at high coverage and a potential surface dimer.     

Photochemistry of refractive index structures in poly(methyl methacrylate) by femtosecond laser irradiation

Femtosecond, subablation threshold photomodification of poly(methyl methacrylate) (PMMA) at 387 nm is explored to enable fabrication of optical components. Volatile fragment analysis (thermal desorption gas chromatography-mass spectrometry) and molecular weight distribution monitoring (size exclusion chromatography) suggest photochemical modification, involving direct cleavage of the polymer backbone and propagation via chain unzipping under formation of monomers, similar to the pyrolytic degradation of PMMA. Waveguides were produced in undoped, clinical-grade PMMA, showing an increased refractive index in the laser focal region (Dnmax=4x10(-3)).     

Ce(IV) complexes with donor-functionalized alkoxide ligands: improved precursors for chemical vapor deposition of CeO2

Thin films of ceria (CeO(2)) have many applications, and their synthesis by liquid-injection MOCVD (metal-organic chemical vapor deposition) or ALD (atomic layer deposition) requires volatile precursor compounds. Here we report the synthesis of a series of homoleptic and heteroleptic Ce(IV) complexes with donor-functionalized alkoxide ligands mmp (1-methoxy-2-methylpropan-2-olate), dmap (1-(dimethylamino)propan-2-olate), and dmop (2-(4,4-dimethyl-4,5-dihydrooxazol-2-yl)propan-2-olate) and their potential as precursors for MOCVD and ALD of CeO(2). New complexes were synthesized by alcohol exchange reactions with [Ce(OBu(t))(4)]. [Ce(mmp)(4)] and [Ce(dmap)(4)] were both found to be excellent precursors for liquid-injection MOCVD of CeO(2), depositing high purity thin films with very low carbon contamination, and both have a large temperature window for diffusion controlled growth (350-600 °C for [Ce(mmp)(4)]; 300-600 °C for [Ce(dmap)(4)]). [Ce(mmp)(4)] is also an excellent precursor for liquid-injection ALD of CeO(2) using H(2)O as oxygen source and demonstrates self-limiting growth from 150 to 350 °C. [Ce(dmap)(4)] has lower thermal stability than [Ce(mmp)(4)] and does not show self-limiting growth in ALD. Heteroleptic complexes show a tendency to undergo ligand redistribution reactions to form mixtures in solution and are unsuitable as precursors for liquid-injection CVD.     

Synthesis of (-)-α-kainic acid via TMSCl-promoted Pd-catalyzed zinc-ene cyclization of an allyl acetate

A highly practical synthesis of enantiopure (-)-α-kainic acid is accomplished in 37% overall yield, using 13 linear steps and a minimum of chromatographic separations via an unprecedented TMSCl-promoted palladium-catalyzed zinc-ene cyclization of an allyl acetate.     

SU(2)-invariant continuum theory for an unconventional phase transition in a three-dimensional classical dimer model

We derive a continuum theory for the phase transition in a classical dimer model on the cubic lattice, observed in recent Monte Carlo simulations. Our derivation relies on the mapping from a three-dimensional classical problem to a two-dimensional quantum problem, by which the dimer model is related to a model of hard-core bosons on the kagome lattice. The dimer-ordering transition becomes a superfluid-Mott insulator quantum phase transition at fractional filling, described by an SU(2)-invariant continuum theory.     

Excitations of one-dimensional Bose-Einstein condensates in a random potential

We examine bosons hopping on a one-dimensional lattice in the presence of a random potential at zero temperature. Bogoliubov excitations of the Bose-Einstein condensate formed under such conditions are localized, with the localization length diverging at low frequency as l(omega) approximately 1/omega(alpha). We show that the well-known result alpha=2 applies only for sufficiently weak random potential. As the random potential is increased beyond a certain strength, alpha starts decreasing. At a critical strength of the potential, when the system of bosons is at the transition from a superfluid to an insulator, alpha=1. This result is relevant for understanding the behavior of the atomic Bose-Einstein condensates in the presence of random potential, and of the disordered Josephson junction arrays.