Molecular and Electronic Structure of Electroactive Self-Assembled Monolayers

Self-assembled monolayers (SAMs) containing electroactive functional groups are excellent model systems for the formation of electronic devices by self-assembly. In particular ferrocene-terminated alkanethiol SAMs have been extensively studied in the past. However, there are still open questions related with their electronic structure including the influence of the ferrocene group in the SAM-induced work function changes of the underlying metal. We have thus carried out a thorough experimental and theoretical investigation in order to determine the molecular and electronic structure of ferrocene-terminated alkanethiol SAMs on Au surfaces. In agreement with previous studies we found that the Fc-containing alkanethiol molecules adsorb forming a thiolate bond with the Au surface with a molecular geometry 30 degrees tilted with respect to the surface normal. Measured surface coverages indicate the formation of a compact monolayer. On the other hand, contrary with previous observations, we found that the ferrocene group has little influence on the observed work function decrease which is largely determined by the alkanethiol. Furthermore, the ferrocene moiety lies 14 Å above the metal surface covalently bonded to the alkanethiol SAM and its HOMO is located at -1.6 eV below the Fermi level. Our results provide new valuable insight into the molecular and electronic structure of electroactive SAMs which are of fundamental importance in the field of molecular electronics.Fil: Méndez de Leo, Lucila Paula. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: de la Llave, Ezequiel Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Scherlis Perel, Damian Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Williams, Federico Jose. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentin

The HERMIT in the machine: a plugin for the interactive transformation of GHC core language programs

The importance of reasoning about and refactoring programs is a central tenet of functional programming. Yet our compilers and development toolchains only provide rudimentary support for these tasks. This paper introduces a programmatic and compiler-centric interface that facilitates refactoring and equational reasoning. To develop our ideas, we have implemented HERMIT, a toolkit enabling informal but systematic transformation of Haskell programs from inside the Glasgow Haskell Compiler’s optimization pipeline. With HERMIT, users can experiment with optimizations and equational reasoning, while the tedious heavy lifting of performing the actual transformations is done for them. HERMIT provides a transformation API that can be used to build higher-level rewrite tools. One use-case is prototyping new optimizations as clients of this API before being committed to the GHC toolchain. We describe a HERMIT application - a read-eval-print shell for performing transformations using HERMIT. We also demonstrate using this shell to prototype an optimization on a specific example, and report our initial experiences and remaining challenges

The Politics of Federalism in Argentina: Implications for Governance and Accountability

This paper contributes to an agenda that views the effects of policies and institutional reforms as dependent on the structure of political incentives for national and subnational political actors. The paper studies political incentive structures at the subnational level and the mechanisms whereby they affect national-level politics and policymaking at the national level in Argentina, a highly decentralized middle-income democracy, Argentina. The Argentine political system makes subnational political power structures very influential in national politics. Moreover, most Argentine provinces are local bastions of power dominated by entrenched elites, characterized by scarce political competition, weak division of powers, and clientelistic political linkages. Political dominance in the provinces and political importance at the national level reinforce each other, dragging the Argentine political and policymaking system towards the practices and features of its most politically backward regions

Freezing, melting and structure of ice in a hydrophilic nanopore

The nucleation, growth, structure and melting of ice in 3 nm diameter hydrophilic nanopores are studied through molecular dynamics simulations with the mW water model. The melting temperature of water in the pore was Tporem = 223 K, 51 K lower than the melting point of bulk water in the model and in excellent agreement with experimental determinations for 3 nm silica pores. Liquid and ice coexist in equilibrium at the melting point and down to temperatures as low as 180 K. Liquid water is located at the interface of the pore wall, increasing from one monolayer at the freezing temperature, Tporef = 195 K, to two monolayers a few degrees below Tporem. Crystallization of ice in the pore occurs through homogeneous nucleation. At the freezing temperature, the critical nucleus contains ∼75 to 100 molecules, with a radius of gyration similar to the radius of the pore. The critical nuclei contain features of both cubic and hexagonal ice, although stacking of hexagonal and cubic layers is not defined until the nuclei reach ∼150 molecules. The structure of the confined ice is rich in stacking faults, in agreement with the interpretation of X-ray and neutron diffraction experiments. Though the presence of cubic layers is twice as prevalent as hexagonal ones, the crystals should not be considered defective Ic as sequences with more than three adjacent cubic (or hexagonal) layers are extremely rare in the confined ice.Fil: Moore, Emily B.. University of Utah; Estados UnidosFil: de la Llave, Ezequiel Pablo. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Welke, Kai. University of Utah; Estados UnidosFil: Scherlis Perel, Damian Ariel. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Molinero, Valeria. University of Utah; Estados Unido