Interaction of H-2 with transition metal homonuclear dimers Cu-2, Ag-2, Au-2 and heteronuclear dimers PdCu, PdAg and PdAu

The reaction mechanisms of the H-2 with the homonuclear dimers M-2 (Cu, Ag, Au) and the heteronuclear dimers PdM (M = Cu, Ag, Au) were studied by use of density functional theory. For the H-2 reactions with homonuclear dimers M-2 (Cu, Ag, Au), it was found that it is easier for Au-2 to dissociate the hydrogen molecule compared with Cu-2 and Ag-2. For H-2 reactions with the heteronuclear dimers PdM (M = Cu, Ag, An), the hydrogen molecule can be easily dissociated at Pd site, rather than at noble metal site.

Density functional study of the second row transition metal dimers

Equilibrium geometries, vibrational frequencies and dissociation energies of the second row transition metal dimers (from Y-2 to Cd-2 except Tc-2) ere studied by use of density functional methods B3LYP, BLYP, B3PW91, BHLYP, BP86, B3P86, SVWN, MPW1PW91 and PBE1PBE. The accuracy DFT methods is found to be highly dependent on the functional employed, in particular for vibrational frequency and dissociation energy. In most cases, the predicted bond distance is in general agreement with experiment and previous theoretical results. For van der Waals dimer Cd-2, B3LYP and BLYP have excellent performance in predicting the bond distance. For Ag-2, all density functional methods used in this study perform well in producing the bond distance, vibrational frequency and dissociation energy.

Density-functional study of lanthanum, ytterbium, and lutetium dimers

La-2, Yb-2, and Lu-2 have been studied by use of the density-functional methods B3LYP, BLYP, B3PW91, BHLYP, BP86, B3P86, MPW1PW91, and PBE1PBE. In these density-functional methods, the exchange functional is from either Becke's three-parameter HF-DFT hybrid exchange functional (B3), pure DFT exchange functional of 1988 (B), a modification of the half-and-half HF/DFT hybrid method (BH), Perdew-Wang 1991 (PW91), or Barone's modified PW91 (MPW1), while the correlation functional is from either Lee, Yang, and Parr (LYP), Perdew-Wang 1991 (PW91), or Perdew 86 (P86). PBE1PBE is the generalized-gradient-approximation exchange-correlation functional of Perdew, Burke, and Ernzerhof. For La-2, the calculated bond distance is in reasonable agreement with the experiment, but the calculated vibrational frequency is underestimated significantly compared with the experiment. Only BP86 and B3P86 have the best performance in reproducing the experimental dissociation energy for La-2. For the van der Waals dimer Yb-2, three functionals, B3LYP, BLYP, and BHLYP have excellent performance in reproducing the spectroscopic constants compared with both the experiment and previous theoretical studies.

Novel polyoxometalate-templated, 3-D supramolecular networks based on lanthanide dimers: Synthesis, structure, and fluorescent properties of [Ln(2)(DNBA)(4)(DMF)(8)][Mo6O19] (DNBA=3,5-dinitrobenzoate)

The spherical Lindquist type polyoxometalate, Mo6O192-, has been used as a noncoordinating anionic template for the construction of novel three-dimensional lanthanide-aromatic monocarboxylate dimer supramolecular networks [Ln(2)(DNBA)(4)(DMF)(8)][Mo6O19] (Ln = La 1, Ce 2, and Eu 3, DNBA = 3,5-dinitrobenzoate, DMF = dimethylformamide). The title compounds are characterized by elemental analyses, IR, and single-crystal X-ray diffractions. X-ray diffraction experiments reveal that two Ln(III) ions are bridged by four 3,5-dinitrobenzoate anions as asymmetrically bridging ligands, leading to dimeric cores, [Ln(2)(DNBA)(4)(DMF)(8)](2+); [Ln(2)(DNBA)(4)(DMF)(8)](2+) groups are joined together by pi-pi stacking interactions between the aromatic groups to form a two-dimensional grid-like network; the 2-D supramolecular layers are further extended into 3-D supramolecular networks with 1-D box-like channels by hydrogen-bonding interactions, in which hexamolybdate polyanions reside. The compounds represent the first examples of 3-D carboxylate-bridged lanthanide dimer supramolecular "host" networks formed by pi-pi stacking and hydrogen-bonding interactions encapsulating noncoordinating "guest" polyoxoanion species. The fluorescent activity of compound 3 is reported.

Direct observation of adsorption sites of protein impurities and their effects on step advancement of protein crystals

We measured noninvasively step velocities of elementary two-dimensional (2D) islands on {110} faces of tetragonal lysozyme crystals, under various supersaturations, by laser confocal microscopy combined with differential interference contrast microscopy. We studied the correlation between the effects of protein impurities on the growth of elementary steps and their adsorption sites on a crystal surface, using three kinds of proteins: fluorescent-labeled lysozyme (F-lysozyme), covalently bonded dimers of lysozyme (dimer), and a 18 kDa polypeptide (18 kDa). These three protein impurities suppressed the advancement of the steps. However, they exhibited different supersaturation dependencies of the suppression of the step velocities. To clarify the cause of this difference, we observed in situ the adsorption sites of individual molecules of F-lysozyme and fluorescent-labeled dimer (F-dimer) on the crystal surface by single-molecule visualization. We found that F-lysozyme adsorbed preferentially on steps (i.e., kinks), whereas F-dimer adsorbed randomly on terraces. Taking into account the different adsorption sites of F-lysozyme and F-dimer, we could successfully explain the different effects of the impurities on the step velocities. These observations strongly suggest that 18 kDa also adsorbs randomly on terraces. Seikagaku lysozyme exhibited a complex effect that could not alone be explained by the two major impurities (dimer and 18 kDa) present in Seikagaku lysozyme, indicating that trace amounts of other impurities significantly affect the step advancement.

Quantum information processing in the wall of cytoskeletal microtubules

Microtubules (MT) are composed of 13 protofilaments, each of which is a series of two-state tubulin dimers. In the MT wall, these dimers can be pictured as "lattice" sites similar to crystal lattices. Based on the pseudo-spin model, two different location states of the mobile electron in each dimer are proposed. Accordingly, the MT wall is described as an anisotropic two-dimensional (2D) pseudo-spin system considering a periodic triangular "lattice". Because three different "spin-spin" interactions in each cell exist periodically in the whole MT wall, the system may be shown to be an array of three types of two-pseudo-spin-state dimers. For the above-mentioned condition, the processing of quantum information is presented by using the scheme developed by Lloyd.

Nonradiative recombination centers in Ga(As,N) and their annealing behavior studied by Raman spectroscopy

Nitrogen-related defects in diluted Ga(As,N) have been detected by Raman scattering in resonance with the localized E+ transition. These defects are attributed to local vibrational modes of nitrogen dimers on Ga- and As-lattice sites. Rapid thermal annealing under appropriate conditions is found to be able to remove the nitrogen dimers. The required minimum annealing temperature coincides with the threshold-like onset of strong, near-band-gap photoluminescence. This finding suggests that the nitrogen dimers are connected with nonradiative recombination centers. (C) 2004 American Institute of Physics.

INVESTIGATION OF THE GROWN DIAMOND (100) SURFACE USING HIGH-RESOLUTION ELECTRON-ENERGY LOSS SPECTROSCOPY

The diamond (100) facets deposited at initial 1.0% CH4 have been investigated using high resolution electron energy loss spectroscopy (HREELS). The diamond (100) facets grown at 800-degrees-C are terminated by CH2 radicals, and there is no detectable frequency shift compared with the characteristic frequencies of molecular subgroup CH2. Beside the CH2 vibration loss, CH bend loss (at 140 meV) of locally monohydrogenated dimer is detected for the diamond (100) facets grown at 1000-degrees-C. Dosing the (100) facets grown at 800-degrees-C with atomic hydrogen at 1*10(-6) mbar, the loss peak at 140 meV appears. It is suggested that there are enough separately vacant sites and uniformly dispersed monohydrogenated dimers on (100) facets. This structure relaxes the steric repulsion between the adjacent hydrogen atoms during the diamond (100) surface growth.

Formation mechanism of defects in annealed InP

Dynamical formation mechanism of defects in the annealed nominally undoped semi-insulating InP obtained by high pressure, high temperature annealing of high purity materials is proposed. Local vibrational modes in tenths of InP samples reveal clearly existence of complexes related to hydrogen. Complexes of vacancy at indium site with one to four hydrogen atoms and isolated hydrogen or hydrogen dimers, complexes of hydrogen with various impurities are investigated by FTIR. Hydrogen can acts as an actuator for generation of antistructure defects. Fully hydrogenated indium vacancy dissociates leaving large lattice relaxation behind, deep donors, mainly larger complexes involving phosphorus at indium site and isolated hydrogen defects are created in nominally undoped InP after annealing. Also created are acceptor levels such as vacancy at indium site. Carrier charge compensation mechanism in nominally undoped InP upon annealing at high temperature is given. Microscopic models of hydrogen related defects are given. Structural, electronic and vibrational properties of LVMs related to hydrogen as well as their temperature effect are discussed.

Hydrogen related defects in InP

Local vibrational modes(LVMs) in tenths of InP samples reveal clearly existence of complexes related to hydrogen. Complexes of vacancy at indium site with one to four hydrogen atom(s) and isolated hydrogen or hydrogen dimers and complexes of hydrogen with various impurities and intrinsic defects are investigated by FTIR. Especially hydrogen related complexes between various transition metals and hydrogen or hydrogen related complexes between hydrogen with point defects. New LVMs related to hydrogen will be reported in this paper. Dynamical formation mechanism of defects in the annealed nominally undoped semiinsulating InP obtained by high pressure, high temperature annealing of ultra purity materials is proposed. Hydrogen can acts as actuator for antistructure defects production. Structural, electronic and vibrational properties of LVMs related to hydrogen as well as their temperature effects are discussed.

On configuration of exchanged La3+ on ZSM-5: A theoretical approach to the improvement in hydrothermal stability of La-modified ZSM-5 zeolite

Density functional calculations have been employed to investigate the locating and binding of lanthanum cation, i.e., La(OH)(2)(+), on HZSM-5 zeolite. Through geometry optimization, it was determined that lanthanum ions are favorably accommodated in the two 6-T rings of the straight channels (Clusters 1 and 2, see Sec. III A for details). Cluster 1 was found to exist in prior to Cluster 2 due to the preference of Al substitution in the T11 site (Cluster 1) rather than in the T8 site (Cluster 2). Geometry-optimization of Cluster 1 containing another two lanthanide ions Nd3+ and Yb3+ was also carried out and it was found that a monotonic decrease in Ln-O bond length will take place as the atomic number increases, conforming well to the rule of lanthanide contraction. Some of the optimized parameters are comparable to the corresponding experimental values in Y zeolite, which confirms that the optimized configurations are acceptable. The average frequencies of hydroxyls attached to La3+ or Yb3+ in Cluster 1 fall at 3609.16 and 3579.76 cm(-1), respectively, with the gap of these two frequencies close to that in the sodalite cage of Y zeolite. Compared to H-form zeolite, the charges on both Al and O atoms in Ln-ZSM-5 zeolite show an obvious increase, which will undoubtedly lead to a stronger mutual interaction and hence enhance the stability of the [AlO4](-) anion. Moreover, the Ln(OH)(2)(+) seem to have thickened the zeolite framework, which can effectively retard the process of dealumination. Through the evaluation of the possibility for dimer formation, it turned out that when the exchange degree arrived to approximately 0.28, lanthanum monomers began to aggregate into dimers, and were completely converted into dimers when the exchange degree approached 0.60. (C) 2003 American Institute of Physics.

Dimerization of 1-butene via zirconium-based Ziegler-Natta catalyst

A zirconium-based Ziegler-Natta catalytic system has been tested in the dimerization of 1-butene. It was found that the concentration of Et2AlCl, Ph3P and PhONa as well as the reaction temperature had great influences on the activity and selectivity of the catalyst. Under the optimum reaction conditions, the conversion of 1-butene is 91.9%, and the selectivity of dimers is 76.7%. Basic ligands such as Ph3P and PhONa can inhibit isomerization of 1-butene to 2-butene effectively. In addition, the metal hydride mechanism was also suggested and some indirect evidence was obtained in favor of this mechanism.

Studies on alkaloids binding to GC-rich human survivin promoter DNA using positive and negative ion electrospray ionization mass spectrometry

Electrospray ionization mass spectrometry (ESI-MS) was used to investigate the binding of 13 alkaloids to two GC-rich DNA duplexes which are critical sequences in human survivin promoter. Negative ion ESI-MS was first applied to screen the binding of the alkaloids to the duplexes. Six alkaloids (including berberine, jatrorrhizine, palmatine, reserpine, berbamine, and tetrandrine) show complexation with the target DNA sequences. Relative binding affinities were estimated from the negative ion ESI data, and the alkaloids show a binding preference to the duplex with higher GC content. Positive ion ESI mass spectra of the complexes were also recorded and compared with those obtained in negative ion mode.

Supramolecular architectures, photophysics, and electroluminescence of 1,3,4-oxadiazole-based iridium(III) complexes: From mu-dichloro bridged dimer to mononuclear complexes

One mu-dichloro bridged diiridium complex and three mononuclear iridium(III) complexes based on the 1,3,4-oxadiazole derivatives as cyclometalated ligands and acetylacetonate (acac) or dithiolates O,O'-diethyldithiophosphate (Et(2)dtp) or N,N'-diethyldithiocarbamate (Et(2)dtc) as ancillary ligands have been synthesized and systematically studied by X-ray diffraction analysis. The results reveal that three mononuclear complexes all adopt distorted octahedral coordination geometry around the iridium center by two chelating ligands with cis-C-C and trans-N-N dispositions, which have the same coordination mode as the diiridium dimer. The dinuclear complex crystallizes in the monoclinic system and space group C2/c, whereas three mononuclear iridium complexes are all triclinic system and space group P(1) over bar. In the stacking structure of the dimer, one-dimensional tape-like chains along the b-axis are formed by hydrogen bondings, which are strengthened by pi stacking interactions between phenyl rings of 1,3,4-oxadiazole ligands. Then these chains assemble a three-dimensional alternating peak and valley fused wave-shape structure. In each stacking structure of three mononuclear complexes, two molecules form a dimer by the C-H center dot center dot center dot O hydrogen bondings, and these dimers are connected by pi stacking interactions along the b-axis, constructing a zigzag chain.