Design of organic semiconductors: tuning the electronic properties of pi-conjugated oligothiophenes with the 3,4-ethylenedioxythiophene (EDOT) building block

Hybrid oligothiophenes based on a various combinations of thiophene and 3,4-ethylenedioxythiophene (EDOT) groups have been synthesized. UV/Vis absorption spectra show that the number and relative positions of the EDOT groups considerably affect the width of the HOMO-LUMO gap and the rigidity of the conjugated system. Analysis of the crystallographic structure of two hybrid quaterthiophenes confirms that insertion of two adjacent EDOT units in the middle of the molecule leads to a self-rigidification of the conjugated systems by intramolecular SO interactions. Cyclic voltammetry data shows that the first oxidation potential of the oligomers decreases with increasing chain length and increasing number of EDOT groups for a given chain length. Electrochemical studies and theoretical calculations show that the positions of the EDOT units in the conjugated chain control the potential difference (DeltaE(p)) between the first and second oxidation steps. Moving the EDOT groups from the outer to the inner positions of the conjugated system increases DeltaE(p). Theoretical calculations confirm that this phenomenon reflects an increase of the intramolecular coulombic repulsion between positive charges in the dication. A thin-film field-effect transistor was fabricated by vacuum sublimation of a pentamer with alternating thiophene-EDOT structure, and the hole mobility was determined.     

Iron-catalyzed homo-coupling of simple and functionalized arylmagnesium reagents

Iron-catalyzed homo-coupling of simple and functionalized arylmagnesium reagents is described. The reaction is highly chemoselective (CN, COOEt and NO(2) groups are tolerated). The procedure was used to perform intramolecular couplings. This cyclization reaction is the key step of the total synthesis of the N-methylcrinasiadine.     

Retardation effects in the rotating string model

A new method to study the retardation effects in mesons is presented. It is based on a generalized rotating string model, in which a nonzero value of the relative time between the quark and the antiquark is allowed. This approach leads to a retardation term in the Hamiltonian which behaves as a perturbation of the nonretarded Hamiltonian and preserves the Regge trajectories for light mesons. The straight-line ansatz is used to describe the string, and the relevance of this approximation is tested. It is shown that the string is actually curved because of retardation, but this bending does not bring a relevant contribution to the energy spectrum of the model.     

Ground State and Charge Renormalization in a Nonlinear Model of Relativistic Atoms

We study the reduced Bogoliubov-Dirac-Fock (BDF) energy which allows to describe relativistic electrons interacting with the Dirac sea, in an external electrostatic potential. The model can be seen as a mean-field approximation of Quantum Electrodynamics (QED) where photons and the so-called exchange term are neglected. A state of the system is described by its one-body density matrix, an infinite rank self-adjoint operator which is a compact perturbation of the negative spectral projector of the free Dirac operator (the Dirac sea). We study the minimization of the reduced BDF energy under a charge constraint. We prove the existence of minimizers for a large range of values of the charge, and any positive value of the coupling constant α. Our result covers neutral and positively charged molecules, provided that the positive charge is not large enough to create electron-positron pairs. We also prove that the density of any minimizer is an L ¹ function and compute the effective charge of the system, recovering the usual renormalization of charge: the physical coupling constant is related to α by the formula α_phys ≃ α(1 + 2α/(3π) log Λ)⁻¹, where Λ is the ultraviolet cut-off. We eventually prove an estimate on the highest number of electrons which can be bound by a nucleus of charge Z. In the nonrelativistic limit, we obtain that this number is  ≤  2Z, recovering a result of Lieb. This work is based on a series of papers by Hainzl, Lewin, Séré and Solovej on the mean-field approximation of no-photon QED.     

On nonlinear gauge theories

In this note, we study non-linear gauge theories for principal bundles, where the structure group is replaced by a Lie groupoid. We follow the approach of Moerdijk–Mr?un and establish its relation with the existing physics literature. In particular, we derive a new formula for the gauge transformation which closely resembles and generalizes the classical formulas found in Yang Mills gauge theories.     

Absence of conventional spin-glass transition in the Ising dipolar system LiHo(x)Y(1-x)F(4)

The magnetic properties of single crystals of LiHo(x)Y(1-x)F(4) with x = 16.5% and x = 4.5% were recorded down to 35 mK using a micro-SQUID magnetometer. While this system is considered as the archetypal quantum spin glass, the detailed analysis of our magnetization data indicates the absence of a phase transition, not only in a transverse applied magnetic field, but also without field. A zero-Kelvin phase transition is also unlikely, as the magnetization seems to follow a noncritical exponential dependence on the temperature. Our analysis thus unmasks the true, short-ranged nature of the magnetic properties of the LiHo(x)Y(1-x)F(4) system, validating recent theoretical investigations suggesting the lack of phase transition in this system.     

Q-switched Yb-doped nonlinear microstructured fiber laser for the emission of broadband spectrum

We report on an innovative configuration of a supercontinuum laser based on an Yb-doped nonlinear microstructured fiber. Due to this particular fiber design combining amplification and nonlinear properties, a wideband output spectrum is generated in the fiber under the Q-switched regime. By exploiting stimulated Brillouin scattering, high peak power pulses are achieved and contribute to a spectral broadening due to a nonlinear wavelength conversion process. Both infrared (1000-1200 nm) and visible (650-750 nm) spectra are generated with an average power of 200 mW.     

A Family of Monotone Quantum Relative Entropies

We study here the elementary properties of the relative entropy ${\mathcal{H}_\varphi(A, B) = {\rm Tr}[\varphi(A) - \varphi(B) - \varphi'(B)(A - B)]}$ for φ a convex function and A, B bounded self-adjoint operators. In particular, we prove that this relative entropy is monotone if and only if φ′ is operator monotone. We use this to appropriately define ${\mathcal{H}_\varphi(A, B)}$ in infinite dimension.     

The Boltzmann equation in classical Yang–Mills theory

We give a detailed derivation of the Boltzmann equation, and in particular its collision integral, in classical field theory. We first carry this out in a scalar theory with both cubic and quartic interactions and subsequently in a Yang–Mills theory. Our method does not rely on a doubling of the fields, rather it is based on a diagrammatic approach representing the classical solution to the problem.