EPR-detected photoinduced electron transfer in three structurally related molecular triads

A comparative electron paramagnetic resonance (EPR) study has been performed on a series of structurally related molecular triads which undergo photoinduced electron transfer and differ one from the other in terms of the acceptor or donor moieties. The molecular triads, C-P-C₆₀, TTF-P-C₆₀ and C-P-P_F, share the same free-base, tetraarylporphyrin (P) as the primary electron donor, which after light excitation initiates the electron transfer process, but differ either in terms of the electron acceptor (fullerene derivative, C₆₀, versus fluorinated free-base porphyrin, P_F), or in terms of the final electron donor (carotenoid polyene, C, versus tetrathiafulvalene, TTF). All these molecular triads can be considered artificial photosynthetic reaction centers in their ability to mimic several key properties of the reaction center primary photochemistry. Photoinduced charge separation and recombination have been followed by time-resolved EPR in a glass of 2-methyltetrahydrofuran and in the nematic phase of the uniaxial liquid crystal E-7. All the triads undergo photoinduced electron transfer, with the generation of charge-separated states in both the low-dielectric environment of the 2-methyl-tetrahydrofuran glass and in anisotropic E-7 medium. Different photochemical pathways have been recognized depending on the specific donor and acceptor moieties constituting the molecular triads. In the presence of the tetrathiafulvalene electron donor singlet- and triplet-initiated electron transfer routes are concurrently active. Recombination to the low-lying carotenoid triplet state occurs in the carotene-based triads, while singlet recombination is the only active route for the TTF-P-C₆₀ triad, where a low-lying triplet state is lacking. Long-lived charge separation has been observed in the case of TTF-P-C₆₀: about 8 μs for the singlet-born radical pair in the glassy isotropic matrix and about 7 μs for the triplet-born radical pair in the nematic phase of E-7. For all the molecular triads, a weak exchange interaction (J?1 G) between the electrons in the final spin-correlated radical pair has been evaluated by simulation of the EPR spectra, providing evidence for superexchange electronic interactions mediated by the tetraarylporphyrin bridge.     

Chromatic and opto-mechanical dispersion of some characteristic parameters of optical fiber undergoing macrobending

Bending of optical fiber leads to an induced-anisotropy in the index profile that influences many important guiding fiber parameters. An analytical method is described for the measurement of refractive-index-wavelength dispersion in bent optical fibers. Multiple-beam Fizeau fringes technique at transmission is used to analyze the opto-mechanical properties and induced-index anisotropy in a standard single-mode fiber undergoes pure mechanical macrobending. The shift in Fizeau fringes is employed to evaluate the dispersion of the cladding material of the bent fiber. The radial variations in Cauchy’s coefficients and the associated variations of some fiber parameters due to macrobending are carried out. The radial profiles of some material parameters such as oscillation energy, dispersion energy, lattice energy and material dispersion are measured as well. The presented method is capable to achieve quantitative and qualitative measurements, which is not available with other methods. The method has a good index resolution in the order of 10⁻⁴ and spatial resolution of 1.3 μm.     

Full-relativistic calculation of electronic structure of Zr2AlC and Zr2AlN

We have employed a full-relativistic version of an all-electron full-potential linearized-augmented plane-wave method in the local density approximation to investigate the electronic structure of nanolaminate Zr₂AlX (X=C and N). The Zr 4d electrons are treated as valence electrons. We have investigated the lattice parameters, bulk moduli, band structures, total and partial densities of states and charge densities. It is demonstrated that the strength and electrical transport properties in these materials are principally governed by the metallic planes.     

Finite-Band Potentials with Trigonal Curves

We construct Dubrovin equations and trace formulas for finite-band operators with trigonal curves and present some examples.     

On Periodic Solutions of Degenerate Singularly Perturbed Linear Systems with Multiple Elementary Divisor

We establish sufficient conditions for the existence and uniqueness of a periodic solution of a system of linear differential equations with a small parameter and a degenerate matrix of coefficients of derivatives in the case of a multiple spectrum of a boundary matrix pencil. We construct asymptotics of this solution.     

Smart Geodesic Tracing in GRworkbench

We have developed a new tool for numerical work in General Relativity: GRworkbench. We discuss how GRworkbench's implementation of a numerically-amenable analogue to Differential Geometry facilitates the development of robust and chart-independent numerical algorithms. We consider, as an example, geodesic tracing on two charts covering the exterior Schwarzschild space-time.     

On the Reality of the Eigenvalues for a Class of -Symmetric Oscillators

 We study the eigenvalue problem with the boundary conditions that decays to zero as z tends to infinity along the rays , where is a real polynomial and . We prove that if for some we have for all , then the eigenvalues are all positive real. We then sharpen this to a larger class of polynomial potentials. In particular, this implies that the eigenvalues are all positive real for the potentials when with , and with the boundary conditions that decays to zero as z tends to infinity along the positive and negative real axes. This verifies a conjecture of Bessis and Zinn-Justin. Received: 16 January 2002 / Accepted: 1 May 2002 Published online: 6 August 2002     

Eigenvalue distributions of random unitary matrices

 Let U be an n × n random matrix chosen from Haar measure on the unitary group. For a fixed arc of the unit circle, let X be the number of eigenvalues of M which lie in the specified arc. We study this random variable as the dimension n grows, using the connection between Toeplitz matrices and random unitary matrices, and show that (X -E [X])/(\Var (X))^1/2 is asymptotically normally distributed. In addition, we show that for several fixed arcs I ₁ , ..., I _m , the corresponding random variables are jointly normal in the large n limit. Received: 15 November 2000 / Revised version: 27 September 2001 / Published online: 17 May 2002     

Inequalities for the Moments and Distribution of the Ladder Height of a Random Walk

We obtain upper bounds for the tail distribution of the first nonnegative sum of a random walk and for the moments of the overshoot over an arbitrary nonnegative level if the expectation of jumps is positive and close to zero. In addition, we find an estimate for the expectation of the first ladder epoch.