An AFM, XPS and electrochemical study of molecular electroactive monolayers formed by wet chemistry functionalization of H-terminated Si(1 0 0) with vinylferrocene

Molecular electroactive monolayers have been produced from vinylferrocene (VFC) via light-assisted surface anchoring to H-terminated n- and p-Si(1 0 0) wafers prepared via wet chemistry, in a controlled atmosphere. The resulting Si-C bound hybrids have been characterized by means of XPS and AFM. Their performance as semiconductor functionalized electrodes and their surface composition have been followed by combining electrochemical and XPS measurements on the same samples, before and after use in an electrochemical cell. White-light photoactivated anchoring at short (1 h) exposure times has resulted in a mild route, with a very limited impact on the initial quality of the silicon substrate. In fact, the functionalized Si surface results negligibly oxidized, and the C/Fe atomic ratio is close to the value expected for the pure molecular species. The VFC/Si hybrids can be described as (η⁵-C₅H₅)Fe²⁺(η⁵-C₅H₄)-CH₂-CH₂-Si species, on the basis of XPS results. Electrochemical methods have been applied in order to investigate the role played by a robust, covalent Si-C anchoring mode towards substrate-molecule electronic communication, a crucial issue for a perspective development of molecular electronics devices. The response found from cyclic voltammograms for p-Si(1 0 0) functionalized electrodes, run in the dark and under illumination, has shown that the electron transfer is not limited by the number of charge carriers, confirming the occurrence of electron transfer via the Si valence band. The hybrids have shown a noticeable electrochemical stability and reversibility under cyclic voltammetry (cv), and the trend in peak current intensity vs. the scan rate was linear. The molecule-Si bond is preserved even after thousands of voltammetric cycles, although the surface coverage, evaluated from cv and XPS, decreases in the same sequence. An increasingly larger surface concentration of Fe³⁺ at the expenses of Fe²⁺ redox centers has been found at increasing number of cv’s, experimentally associated with the growth of silicon oxide. Surface SiO⁻ groups from deprotonated silanol termination, induced by the electrochemical treatments, are proposed as the associated counterions for the Fe³⁺ species. They could be responsible for the observed decrease in the electron transfer rate constant with electrode ageing.     

Stability results for Mountain Pass and Linking type solutions of semilinear problems involving Dirichlet forms

Some stability results for Mountain Pass and Linking type solutions of semilinear problems involving a very general class of Dirichlet forms are stated. The non linear terms are supposed to have a suitable superlinear growth and the family of Dirichlet forms is required to be dominated from below and from above by a fixed diffusion type form. Some concrete examples are also given.     

Semigroups Generated by Ordinary Differential Operators in L 1(I)*

In this paper we give necessary and sufficient conditions for the existence of a C> ₀-semigroup in L ¹(I) (I real interval) generated by a second-order differential operator when suitable boundary conditions at the endpoints are imposed.     

Stable determination of an inhomogeneous inclusion by local boundary measurements

We deal with the problem of determining an inclusion within an electrostatic conductor from boundary measurements. Under mild a priori assumptions we establish optimal stability estimates. Measurements are performed on a portion of the boundary of the conductor.     

Packing into the smallest square: Worst-case analysis of lower bounds

We address the problem of packing a given set of rectangles into the minimum size square. We consider three versions of the problem, arising when the rectangles (i) are squares; (ii) have a fixed orientation; (iii) can be rotated by 90. For each case we study lower bounds, and analyze their worst-case performance ratio. In addition, we evaluate through computational experiments their average performance on instances from the literature.     

A remark on Serrin’s Theorem

An approximation theorem for families of weakly coercive convex functions by means of countably many smooth families of convex functions is proved. As a consequence, the classical “three-fold” lower semicontinuity theorem for integral functionals of the Calculus of Variations by James Serrin is unified in one single statement.     

Ab initio path-integral molecular dynamics

A path-integral molecular dynamics technique for strongly interacting atoms using ab initio potentials derived from density functional theory is implemented. This allows the efficient inclusion of nuclear quantum dispersion in ab initio simulations at finite temperatures. We present an application to the quantum cluster H ₅ ⁺ .     

General theorems and fundamental solutions in the dynamical theory of mixtures

This paper is concerned with the dynamic theory of a binary mixture consisting of a gas and an elastic solid. First, we derive general theorems (reciprocal theorem, uniqueness theorem, minimum principle). The, we establish a Galerkin representation and the fundamental solutions in the case of steady vibrations.Work performed under the auspices of G.N.F.M. of the Italian Research Council (C.N.R.), with the grant 60% M.U.R.S.T. (ITALY).