Reaction dynamics of Mo + O(2) → MoO + O studied by a crossed-beam velocity map imaging technique

The oxidation reaction dynamics of gas-phase molybdenum atoms by oxygen molecules was studied under a crossed-beam condition. The product MoO was detected by a time-of-flight mass spectrometer combined with laser multi-photon ionization. An acceleration lens system designed for the ion-velocity mapping condition, a two-dimensional (2D) detector, and a time-slicing technique were used to obtain the velocity and angular distributions of the products at three collision energies: 10.0, 17.8, and 50.0 kJ/mol. The angular distributions showed forward and backward peaks, whose relative intensities changed by the collision energy. While two peaks had similar intensities at low collision energies, the forward peak became dominant at the highest collision energy, 50 kJ/mol. The product kinetic energy distributions showed a good correlation with the initial collision energies, i.e., almost the same energy as the collision energy appeared as the product kinetic energy. These results suggested that the reaction proceeds via an intermediate complex, and the lifetime of the complex becomes shorter than its rotational period at high collision energy.     

Instantaneous vibrational frequencies of diffusing and desorbing adsorbates: CO/Pt(111)

Electronic excitation of metal by intense laser pulses stimulates nuclear motions of adsorbates through nonadiabatic coupling, resulting in diffusion and desorption of adsorbates. These processes take place via precursor states: adsorbates whose vibrational modes with respect to substrate are highly excited. This paper reports the dynamics of precursor states of CO on Pt(111) probed by use of infrared-visible sum frequency generation with phase-sensitive detection, which allows us to obtain the second-order nonlinear susceptibility and thus the vibrational response function. Without pump pulses at 400 nm, the inverse Fourier transformation of the vibrational response function reveals a free induction decay of vibrational polarization of C-O stretching created by a short infrared pulse. The free induction decay is perturbed when an intense 400-nm pump pulse following the infrared pulse is irradiated, because diffusion and desorption of CO are induced by the pump pulse. The time evolution of instantaneous C-O stretching frequency retrieved from the perturbed free induction decay shows a redshift followed by a rapid reverse shift when the fluence of pump pulse is high enough to desorb CO. This indicates that the frustrated modes of CO is first substantially excited and then the parallel momentum of CO is converted to the normal one through mutual collisions, leading to substantial excitation of the external stretching mode of CO.     

Incorporation of cationic electron donor of Ni-pyridyltetrathiafulvalene with anionic electron acceptor of polyoxometalate

A new salt-[Ni(II)(DMSO)(5)(TTFPy)](2)[α-SiW(12)O(40)] (1)-based on polyoxometalates was prepared by coordinating a cationic electron donor of pyridyltetrathiafulvalene (TTFPy) with Ni(II). Although the TTFPy molecule did not form a salt with the anionic α-[SiW(VI)(12)O(40)](4-) because of the weak charge-transfer (CT) interaction, the coordination of Ni with the pyridyl moiety permitted salt formation driven by electrostatic interaction, giving a single crystal of 1. Crystallographic analysis, UV-vis and IR spectroscopy and electrochemical characterization revealed that the fully oxidized α-[SiW(VI)(12)O(40)](4-) was crystallized with the neutral TTFPy moiety from the acetonitrile solution because of the low electron-withdrawing ability of α-[SiW(VI)(12)O(40)](4-), forming a brown-orange crystal. The crystal colour quickly turned to black by immersing in methanol, due to CT from TTF moiety to α-[SiW(VI)(12)O(40)](4-), which was caused by the solvent effect. Increase in the solvent acceptor number from 18.9 for acetonitrile to 41.3 for methanol resulted in the enhancement of the electron withdrawing ability of α-[SiW(VI)(12)O(40)](4-) by 0.317 V in methanol.     

A rectangular Ni-Fe cluster with unusual cyanide bridges

An asymmetric polycyanide iron complex, K(2)[Fe(III)(L1)(CN)(4)](MeOH) (HL1 = 2,2'-(1H-pyrazole-3,5-diyl)bis-pyridine), was synthesized and its complexation compatibility with nickel ions was examined. Two kinds of enantiomeric nickel-iron squares were obtained in the presence of a chiral bidentate capping ligand. The compounds display unusual cyanide bridge geometry and have ferromagnetic interactions between nickel and iron ions.     

Galvanomagnetic properties of air-stable and highly conductive potassium-intercalated graphite sheet

Magnetoresistance and Hall coefficient of air-stable potassium-intercalated graphite sheets (hereafter abbreviated as K-PGS) were determined at room temperature. The magnitude of the magnetoresistance and the absolute value of Hall coefficient of K-PGS decreased with increasing potassium content of K-PGS, n_K/n_C. Two-carrier model was used for calculating carrier density and mobility. The electron density increased with increasing n_K/n_C: 3.07×10²⁰ cm⁻³ (n_K/n_C=0.005), 5.67×10²⁰ cm⁻³ (n_K/n_C=0.008) and 6.40×10²⁰ cm⁻³ (n_K/n_C=0.011). The value of the electron density of K-PGS with n_K/n_C=0.011 (nominal composition KC₉₁) was about 80% of the reported value, 7.8×10²⁰ cm⁻³, for KC₄₈ (n_K/n_C=0.021) prepared from HOPG (highly oriented pyrolytic graphite). The mobility decreased with increasing n_K/n_C: 2.11×10³ cm² V⁻¹ s⁻¹ (n_K/n_C=0.005), 1.42×10³ cm² V⁻¹ s⁻¹ (n_K/n_C=0.008) and 1.34×10³ cm² V⁻¹ s⁻¹ (n_K/n_C=0.011). The value of the mobility of K-PGS with n_K/n_C=0.011 was about 60% of the reported value (2300 cm² V⁻¹ s⁻¹) for KC₄₈ prepared from HOPG.     

Devil' Staircase and Frustoelectricity in Chiral Smectic-C like Liquid Crystals

Abstract

In 1989, Chandani et al. showed that the tristable switching, already observed by themselves and by others in 4-(1-methylheptyloxycarbonyl) phenyl 4′-octyloxybiphenyl-4-carboxylate (MHPOBC).     

J-PARC E27 Experiment to Search for a Nuclear Kaon Bound State K − pp

In the J-PARC E27 experiment, we search for a K ^? pp bound state via the d(π ⁺, K ⁺) reaction at 1.7 GeV/c at the K1.8 beam line. The binding energy and decay width of the K ^? pp bound state can be obtained in the missing mass measurement with a good energy resolution of 2 MeV/c ². A range counter array (RCA) was constructed to detect the two high-momentum protons from the K ^? pp decay and to reduce the background such as quasi-free hyperon production. Recently, we have carried out a pilot run in June, 2012. The d(π ⁺, K ⁺) missing-mass spectrum has been obtained for the first time. In this report, an overview of the E27 experiment and a preliminary result on this pilot run are presented.     

Moments of a Single Entry of Circular Orthogonal Ensembles and Weingarten Calculus

Consider a symmetric unitary random matrix V = (v _ij )_{1 ≤ i, j ≤ N} from a circular orthogonal ensemble. In this paper, we study moments of a single entry v _ij . For a diagonal entry v _ii , we give the explicit values of the moments, and for an off-diagonal entry v _ij , we give leading and subleading terms in the asymptotic expansion with respect to a large matrix size N. Our technique is to apply the Weingarten calculus for a Haar-distributed unitary matrix.     

Metachromasy Bands of Disk-Like Guests in the Host Lyotropic Liquid Crystal Disodium Chromoglycate-Water

Electronic absorption spectra of Crystal Violet (CV), Malachite Green (MG) and Methylene Blue (MB) have been investigated in the 500–700 nm region using lecithin-water and disodium chromoglycate (DSCG)-water lyotropic liquid crystals as hosts. Metachromasy bands of CV and MG, indicative of associations of guest molecules, are observed even in the mesophase of the DSCG-water system, in spite of the suppression effect of the host which tends to reduce the degree of association of guest molecules with increasing host concentration. This contrasts with the case of a rod-like guest such as MB, where no indication of association of guest molecules is observed in the DSCG lyotropic mesophase. These spectral observations on the guests in the host DSCG lyotropic liquid crystal are explained in terms of some crucial structural parameter of the guests and a lyotropic columnar structure of the host such as that proposed by Attwood et al.     

SEM and TEM Observation of Carbon Nano-Fibers Prepared by Hot Filament Assisted Sputtering

Abstract

Carbon films were prepared by hot filament assisted sputtering. Pure argon was used as the sputtering gas. The substrate temperature was 600 °C and the filament temperature was about 2000 °C. Sample was inhomogeneous. Scanning electron microscope (SEM) and transmission electron microscope (TEM) images showed that some part of films consisted of carbon nano fibers (not hollow but solid). Amorphous and polycrystalline phases were also detected by these measurements. No tube structure was observed by high resolution TEM. The diameter of the fiber was 10–30 nm.