A chromic molybdenum phosphate with a tunnel structure: hydrothermal synthesis and structure of (NH3CH2CH2NH3)(2) center dot (NH3CH2CH2NH2)(3)center dot[NaCr2Mo12O30(PO4)(HPO4)(4)(H2PO4)(3)]center dot 6H(2)O

A chromic molybdenum phosphate, (NH3CH2CH2NH3)(2).(NH3CH2CH2NH2)(3).[NaCr2Mo12O30(PO4)(HPO4)(3)]. 6H(2)O, involving molybdenum present in V oxidation, has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction and IR spectrum. Deep brown-red crystals are formed in the triclinic system, space group P (1) over bar, a = 12.067(2), b = 14.677(3), c = 21.290(2) Angstrom, alpha = 80.940(10)degrees, beta = 82.960(10)degrees, gamma = 76.61(2)degrees. The structure of the title compound may be considered to be two [Mo6O15(HPO4)(H2PO4)(3)](5-) units bonded to a chromic atom, although several P-O groups are not protonated on account of coordination with a Na+ cation. The one-dimensional tunnels were formed in the solid of the title compound. (C) 2000 Elsevier Science B.V. All rights reserved.

A manganese molybdenum phosphate with a tunnel: hydrothermal synthesis, structure and catalytic properties of (NH3CH2CH2NH3)(10-)H3O)(3)(H5O2)Na-2[MnMo12O24(OH)(6)(PO4)(4)(PO3OH)(4)]-[MnMo12O24(OH)(6)(PO4)(6)(PO3OH)(2)] center dot 9H(2)O

A manganese molybdenum phosphate, (NH3CH2CH2NH3)(10)(H3O)(3)(H5O)Na-2[MnMo12O24(OH)(6) (PO4)(4)(PO3OH)(4)][MnMo12O24 (OH)(6)(PO4)(6)(PO3OH)(2)]. 9H(2)O, has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. The structure of this compound may be considered to be two [Mo6O12(OH)(3)(PO4)(2)(HPO4)(2)](7-) units bonded together by a manganese atom, although several P-O groups are not protonated on account of coordination to a Na+ cation. One-dimensional tunnels were formed in the solid. A probe reaction of the oxidation of acetaldehyde with H2O2 using this compound as catalyst was carried out in a liquid-solid system, showing that the manganese molybdenum phosphate has high catalytic activity in the reaction.

A nickel molybdenum phosphate with tunnel: Hydrothermal synthesis and structure of (NH3CH2CH2NH3)(4)center dot(NH3CH2CH2NH2)center dot Na center dot[Ni2Mo12O30(PO4)(HPO4)(4)(H2PO4)(3)]center dot 6H(2)O

A nickel molybdenum phosphate, (NH3CH2CH2NH3)(4).(NH3CH2CH2NH2). Na .[Ni2Mo12O30(PO4)(HPO4)(4)(H2PO4)(3)]. 6H(2)O, invoicing molybdenum present in V oxidation, has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. Deep brown-red crystals are formed in the triclinic system, space group P (1) over bar, a = 12,011(2), b = 14,612(3), c = 21.252(4) Angstrom, alpha = 80.54(2)degrees, beta = 83.10(2)degrees, gamma = 76.29(2)degrees, V = 3561.4(12) Angstrom(3), Z = 2, lambda(MoK alpha) = 0.71073 Angstrom (R(F) = 0.0529 for 9880 reflections), Data mere collected on a Siemens P4 diffractometer at 20 degrees C in the range of 1.75 degrees < theta < 23.02 degrees using the omega-scan technique. The structure was solved by direct methods using the program SHELXTL-93 and refined with the method of fun-matrix least-squares on F-2. The structure of the title compound may be considered to be two [Mo6O15(HPO4)(H2PO4)(3)](5-) units bonded together with a nickel atom, although several P-O groups are not protonated on account of coordination with a Na+ cation, The one-dimensional tunnels were formed in the solid of the title compound. A probe reaction of the oxidation of acetaldehyde with H2O2 using the title compound as catalyst was carried out in a liquid- solid system, showing that the title compound had high catalytic activity in the reaction, (C) 1999 Academic Press.

A ferric molybdenum phosphate with a tunnel: hydrothermal synthesis and structure of (NH3CH2CH2NH3)(2)center dot(NH3CH2CH2NH2)(3)center dot Na center dot[Fe2Mo12O30(PO4)(HPO4)(4)(H2PO4)(3)]center dot 7H(2)O

A new ferric molybdenum phosphate containing a tunnel structure and crystallographically different clusters has been hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction. A probe reaction of the oxidation of acetaldehyde with H2O2 using the tide compound as catalyst was carried out in a liquid-solid system, showing that the title compound had high catalytic activity in the reaction. (C) 1998 Elsevier Science S.A. All rights reserved.

Properties of molecules in tunnel junctions

Molecular tunnel junctions involve studying the behaviour of a single molecule sandwiched between metal leads. When a molecule makes contact with electrodes, it becomes open to the environment which can heavily influence its properties, such as electronegativity and electron transport. While the most common computational approaches remain to be single particle approximations, in this thesis it is shown that a more explicit treatment of electron interactions can be required. By studying an open atomic chain junction, it is found that including electron correlations corrects the strong lead-molecule interaction seen by the ΔSCF approximation, and has an impact on junction I − V properties. The need for an accurate description of electronegativity is highlighted by studying a correlated model of hexatriene-di-thiol with a systematically varied correlation parameter and comparing the results to various electronic structure treatments. The results indicating an overestimation of the band gap and underestimation of charge transfer in the Hartree-Fock regime is equivalent to not treating electron-electron correlations. While in the opposite limit, over-compensating for electron-electron interaction leads to underestimated band gap and too high an electron current as seen in DFT/LDA treatment. It is emphasised in this thesis that correcting electronegativity is equivalent to maximising the overlap of the approximate density matrix to the exact reduced density matrix found at the exact many-body solution. In this work, the complex absorbing potential (CAP) formalism which allows for the inclusion metal electrodes into explicit wavefunction many-body formalisms is further developed. The CAP methodology is applied to study the electron state lifetimes and shifts as the junction is made open.

Effet du bromouracile sur la synthèse et la structure des protéines de phages

Doctorat en Sciences

Atomic excitation during recollision-free ultrafast multi-electron tunnel ionization

Modern intense ultrafast pulsed lasers generate an electric field of sufficient strength to permit tunnel ionization of the valence electrons in atoms(1). This process is usually treated as a rapid succession of isolated events, in which the states of the remaining electrons are neglected(2). Such electronic interactions are predicted to be weak, the exception being recollision excitation and ionization caused by linearly polarized radiation(3). In contrast, it has recently been suggested that intense field ionization may be accompanied by a two-stage 'shake-up' reaction(4). Here we report a unique combination of experimental techniques(5-8) that allows us to accurately measure the tunnel ionization probability for argon exposed to 50-fs laser pulses. Most significantly for the current study, this measurement is independent of the optical focal geometry(7,8), equivalent to a homogenous electric field. Furthermore, circularly polarized radiation negates recollision. The present measurements indicate that tunnel ionization results in simultaneous excitation of one or more remaining electrons through shake-up(9). From an atomic physics standpoint, it may be possible to induce ionization from specific states, and will influence the development of coherent attosecond extreme-ultraviolet-radiation sources(10). Such pulses have vital scientific and economic potential in areas such as high-resolution imaging of in vivo cells and nanoscale extreme-ultraviolet lithography.

On the recollision-free excitation of krypton during ultrafast multi-electron tunnel ionization

The probability of multiple ionization of krypton by 50 femtosecond circularly polarized laser pulses, independent of the optical focal geometry, has been obtained for the first time. The excellent agreement over the intensity range 100 TW cm-2 to 100 PW cm-2 with the recent predictions of Kornev et al (2003 Phys. Rev. A 68 043414) provides the first experimental confirmation that non-recollisional electronic excitation can occur in strong-field ionization. This is particularly true for higher stages of ionization, when the laser intensity exceeds 10 PW cm-2 as the energetic departure of the ionized electron(s) diabatically distorts the wavefunctions of the bound electrons. By scaling the probability of ionization by the focal volume, we discuss why this mechanism was not apparent in previous studies.

Design and testing of transonic linear cascade tunnel with optimized slotted walls

In linear cascade wind tunnel tests, a high level of pitchwise periodicity is desirable to reproduce the azimuthal periodicity in the stage of an axial compressor or turbine. Transonic tests in a cascade wind tunnel with open jet boundaries have been shown to suffer from spurious waves, reflected at the jet boundary, that compromise the flow periodicity in pitch. This problem can be tackled by placing at this boundary a slotted tailboard with a specific wall void ratio s and pitch angle a. The optimal value of the s-a pair depends on the test section geometry and on the tunnel running conditions. An inviscid two-dimensional numerical method has been developed to predict transonic linear cascade flows, with and without a tailboard, and quantify the nonperiodicity in the discharge. This method includes a new computational boundary condition to model the effects of the tailboard slots on the cascade interior flow. This method has been applied to a six-blade turbine nozzle cascade, transonically tested at the University of Leicester. The numerical results identified a specific slotted tailboard geometry, able to minimize the spurious reflected waves and regain some pitchwise flow periodicity. The wind tunnel open jet test section was redesigned accordingly. Pressure measurements at the cascade outlet and synchronous spark schlieren visualization of the test section, with and without the optimized slotted tailboard, have confirmed the gain in pitchwise periodicity predicted by the numerical model. Copyright © 2006 by ASME.