Ultrafast voltammetry for probing interfacial electron transfer in molecular wires.

Electron transfer inside self-assembled monolayers made from complex redox-active oligophenylenevinylene molecular wires is examined by ultrafast cyclic voltammetry. Rate constants above 10(6) s(-1) are measured when the electroactive moieties are easily accessible to counterions from the electrolyte. These counterion movements are necessary to compensate the local charge created upon electron transfer. Conversely, if the redox center is buried within long hydrophobic diluents, the counterion movement towards the redox entity becomes rate limiting, thus drastically altering the rate magnitude and its physical meaning. This change in the mechanism is examined both for superexchange or when one electron-hopping step is involved.     

How the Jones polynomial gives rise to physical states of quantum general relativity

Solutions to both the diffeomorphism and the hamiltonian constraint of quantum gravity have been found in the loop representation, which is based on Ashtekar's new variables. While the diffeomorphism constraint is easily solved by considering loop functionals which are knot invariants, there remains the puzzle why several of the known knot invariants are also solutions to the hamiltonian constraint. We show how the Jones polynomial gives rise to an infinite set of solutions to all the constraints of quantum gravity thereby illuminating the structure of the space of solutions and suggesting the existance of a deep connection between quantum gravity and knot theory at a dynamical level.This essay received the third award from the Gravity Research Foundation, 1992-Ed     

A photochemical activation scheme of inert dinitrogen by dinuclear Ru(II) and Fe(II) complexes

A general photochemical activation process of inert dinitrogen coordinated to two metal centers is presented on the basis of high-level DFT and ab initio calculations. The central feature of this activation process is the occupation of an antibonding pi* orbital upon electronic excitation from the singlet ground state S0 to the first excited singlet state S1. Populating the antibonding LUMO weakens the triple bond of dinitrogen. After a vertical excitation, the excited complex may structurally relax in the S1 state and approaches its minimum structure in the S1 state. This excited-state minimum structure features the dinitrogen bound in a diazenoid form, which exhibits a double bond and two lone pairs localized at the two nitrogen atoms, ready to be protonated. Reduction and de-excitation then yield the corresponding diazene complex; its generation represents the essential step in a nitrogen fixation and reduction protocol. The consecutive process of excitation, protonation, and reduction may be rearranged in any experimentally appropriate order. The protons needed for the reaction from dinitrogen to diazene can be provided by the ligand sphere of the complexes, which contains sulfur atoms acting as proton acceptors. These protonated thiolate functionalities bring protons close to the dinitrogen moiety. Because protonation does not change the pi*-antibonding character of the LUMO, the universal and well-directed character of the photochemical activation process makes it possible to protonate the dinitrogen complex before it is irradiated. The pi*-antibonding LUMO plays the central role in the activation process, since the diazenoid structure was obtained by excitation from various occupied orbitals as well as by a direct two-electron reduction (without photochemical activation) of the complex; that is, the important bending of N2 towards a diazenoid conformation can be achieved by populating the pi*-antibonding LUMO.     

Bonding in a borylene complex investigated by photoionization and dissociative photoionization

The borylene complex [(OC)(5)Cr=B=N(SiMe(3))(2)] has been investigated by using threshold photoelectron-photoion coincidence spectroscopy with synchrotron radiation. The ionization energy of the parent complex and the 0?K appearance energies of the sequential CO loss channels have been determined. The derived bond-dissociation energies are used to discuss bonding and energetics in this compound.     

Changes in the gradient percolation transition caused by an Allee effect

The establishment and spreading of biological populations depends crucially on population growth at low densities. The Allee effect is a problem in those populations where the per capita growth rate at low densities is reduced. We examine stochastic spatial models in which the reproduction rate changes across a gradient g so that the population undergoes a 2D-percolation transition. Without the Allee effect, the transition is continuous and the width w of the hull scales as in conventional (i.e., uncorrelated) gradient percolation, w ∝ g(-0.57). However, with a strong Allee effect the transition is first order and w ∝ g(-0.26).     

Self-organized patterning on Si(001) by ion sputtering with simultaneous metal incorporation

This report focuses on the effect of simultaneous Fe incorporation in the self-organized pattern formation on Si(001) by low-energy ion-beam sputtering. Experimental observations giving evidence for the correlation between different ion-beam parameters, Fe concentration on the substrate, and the resulting topography are shown. It was observed that the incorporation of Fe affects the evolution of the topography and it is a requisite for the formation of ripples at near-normal incidence. It is shown also that Fe is not homogeneously distributed on the surface, but there is a higher concentration at the crests of the ripples than at the valleys. For the experimental setup used for this study, the Fe flux that reaches the surface is determined mainly by the acceleration voltage (U _acc), while the ion energy (E _ion) and ion-beam incidence angle (α) control the concentration of Fe in the steady state. The adjustment of these operational parameters of the ion source enables the fine-tuning of surface patterns.     

Convariant q-Differential Calculus and its Deformations at qN = 1

We construct the generalized version of covariant Z₃-graded differential calculus introduced by one of us (R.K.) and then extend it to the case of arbitrary Z_N grading. Here our main purpose is to establish the recurrence formulae for the Nth power of covariant q-differential D_q=d_q + A and to analyze more closely the particular case of q being an Nth primitive root of unity. The generalized notions of connection and curvature are introduced and several examples of realization are displayed for N=3 and 4. Finally we briefly discuss the idea of infinitesimal deformations of the parameter q in the complex plane.