9,346 research outputs found
Oxygen vacancies in strained SrTiO thin films: formation enthalpy and manipulation
We report the enthalpy of oxygen vacancy formation in thin films of
electron-doped SrTiO, under different degrees of epitaxial stress. We
demonstrate that both compressive and tensile strain decrease this energy at a
very similar rate, and promote the formation of stable doubly ionized oxygen
vacancies. Moreover, we also show that unintentional cationic vacancies
introduced under typical growth conditions, produce a characteristic rotation
pattern of TiO octahedra. The local concentration of oxygen vacancies can
be modulated by an electric field with an AFM tip, changing not only the local
electrical potential, but also producing a non-volatile mechanical response
whose sign (up/down) can be reversed by the electric field.Comment: Physical Review B (accepted for publication
Model Calculation of Electron-Phonon Couplings in a Dimer with a Non-Degenerate Orbital
We evaluate all the electron-phonon couplings derived from the one-body
electronic interactions, in both the adiabatic and extreme non-adiabatic limit,
for a dimer with a non-degenerate orbital built from atomic wave functions of
Gaussian shape. We find largely different values of the coupling parameters in
the two cases, as well as different expressions of the corresponding terms in
the Hamiltonian.Comment: 5 postscript figure
Modification of chiral dimethyl tartrate through transesterification : immobilisation on POSS and enantioselectivity reversion in Sharpless asymmetric epoxidation
Modification of dimethyl tartrate has been investigated through transesterification with aminoalcohols to provide reactive functionalities for the covalent bonding of chiral tartrate to polyhedral oligomeric silsesquioxanes. The transesterification of dimethyl tartrate has been widely studied by means of using different catalytic systems and reaction conditions. Through the proper selection of both, the catalytic system and the reaction conditions, it is possible to achieve the mono- or the bis-substituted tartrate derivative as sole products. All the intermediate chiral tartrate-derived ligands were successfully used in the homogeneous enantioselective epoxidation of allylic alcohols providing moderate enantiomeric excess over the products. Attached amine groups have been used to support the modified tartrate ligands onto a haloaryl-functionalized silsesquioxane moiety. This final chiral tartrate ligand displays enantioselectivity reversion in the asymmetric epoxidation of allylic alcohols with regards to the starting dimethyl tartrate ligand, having both molecules them the same chiral sign. However, the POSS-containing ligand can be easily recovered in almost quantitative yield and reused in asymmetric epoxidation reactions. In addition, recovered silsesquioxane-pendant ligand, though displaying decreasing catalytic activity in recycling epoxidation tests, showed very stable enantioselective behavior
Biomimetic flow fields for proton exchange membrane fuel cells: A review of design trends
Bipolar Plate design is one of the most active research fields in Polymer Electrolyte Membrane Fuel Cells (PEMFCs) development. Bipolar Plates are key components for ensuring an appropriate water management within the cell, preventing flooding and enhancing the cell operation at high current densities. This work presents a literature review covering bipolar plate designs based on nature or biological structures such as fractals, leaves or lungs. Biological inspiration comes from the fact that fluid distribution systems found in plants and animals such as leaves, blood vessels, or lungs perform their functions (mostly the same functions that are required for bipolar plates) with a remarkable efficiency, after millions of years of natural evolution. Such biomimetic designs have been explored to date with success, but it is generally acknowledged that biomimetic designs have not yet achieved their full potential. Many biomimetic designs have been derived using computer simulation tools, in particular Computational Fluid Dynamics (CFD) so that the use of CFD is included in the review. A detailed review including performance benchmarking, time line evolution, challenges and proposals, as well as manufacturing issues is discussed.Ministerio de Ciencia, Innovación y Universidades ENE2017-91159-EXPMinisterio de EconomÃa y Competitividad UNSE15-CE296
The Quest for Palladium-Catalysed Alkyl-Nitrogen Bond Formation
Our interest in the development of transition-metal catalysis for the realisation of vicinal diamination reactions of alkenes started about a decade ago. A number of successful transformations in this area have been developed using palladium catalysis. As a challenging aspect of major importance, the palladium-catalysed coupling of alkyl–nitrogen bonds constitutes the second step in diaminations of alkenes. We here discuss the details that led us to consider high-oxidation-state palladium catalysis as a key feature in such C–N bond-forming reactions. This work discusses both our own contributions and the ones from colleagues and combines the discussion of catalytic reactions and stoichiometric control experiments. It demonstrates that reductive alkyl–nitrogen bond formation from palladium(IV) proceeds with a low activation barrier and through a linear transition state of nucleophilic displacement
A general framework for nonholonomic mechanics: Nonholonomic Systems on Lie affgebroids
This paper presents a geometric description of Lagrangian and Hamiltonian
systems on Lie affgebroids subject to affine nonholonomic constraints. We
define the notion of nonholonomically constrained system, and characterize
regularity conditions that guarantee that the dynamics of the system can be
obtained as a suitable projection of the unconstrained dynamics. It is shown
that one can define an almost aff-Poisson bracket on the constraint AV-bundle,
which plays a prominent role in the description of nonholonomic dynamics.
Moreover, these developments give a general description of nonholonomic systems
and the unified treatment permits to study nonholonomic systems after or before
reduction in the same framework. Also, it is not necessary to distinguish
between linear or affine constraints and the methods are valid for explicitly
time-dependent systems.Comment: 50 page
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