Phonon dynamics and electron-phonon coupling in pristine picene

The paper reports a complete analysis of the phonon structure of crystalline picene, a recently announced organic semiconductor. Both lattice and intramolecular vibrations are investigated. An exhaustive assignment of lattice phonons is obtained through polarized Raman spectra assisted by lattice dynamics calculations based on a well tested atom-atom potential model. Raman, infrared spectra and density functional (DFT) calculations are used for the characterization of intramolecular modes. Coupling between low-frequency molecular vibrations and lattice phonons is accounted for. Molecule-to-molecule transfer integrals, as well as the Peierls and Holstein (non-local and local) coupling constants, are evaluated through the semiempirical method INDO/S (Intermediate Neglect of Differential Overlap with Spectroscopic parametrization).     

Electrochemical Approach for the Production of Layered Double Hydroxides with a Well-Defined Co/MeIII Ratio

Layered double hydroxides (LDHs) have been widely studied for their plethora of fascinating features and applications. The potentiostatic electrodeposition of LDHs has been extensively applied in the literature as a fast and direct method to substitute classical chemical routes. However, the electrochemical approach does not usually allow for a fine control of the M^II/M^III ratio in the synthesized material. By employing a recently proposed potentiodynamic method, LDH films of controlled composition are herein prepared with good reproducibility, using different ratios of the trivalent (Fe or Al) to bivalent (Co) cations in the electrolytic solution. All the obtained materials are shown to be effective oxygen evolution reaction (OER) catalysts, and are thoroughly characterized by a multi-technique approach, including FE-SEM, XRD, Raman, AES and a wide range of electrochemical procedures.     

High-pressure dissociation of crystalline para-diiodobenzene: optical experiments and Car-Parrinello calculations

We have investigated the high-pressure properties of the molecular crystal para-diiodobenzene, by combining optical absorption, reflectance, and Raman experiments with Car-Parrinello simulations. The optical absorption edge exhibits a large red shift from 4 eV at ambient conditions to about 2 eV near 30 GPa. Reflectance measurements up to 80 GPa indicate a redistribution of oscillator strength toward the near-infrared. The calculations, which describe correctly the two known molecular crystal phases at ambient pressure, predict a nonmolecular metallic phase, stable at high pressure. This high-density phase is characterized by an extended three-dimensional network, in which chemically bound iodine atoms form layers connected by hydrocarbon bridges. Experimentally, Raman spectra of samples recovered after compression show vibrational modes of elemental solid iodine. This result points to a pressure-induced molecular dissociation process which leads to the formation of domains of iodine and disordered carbon.     

Do computed crystal structures of nonpolar molecules depend on the electrostatic interactions? The case of tetracene

We present a strategy for comparing the global properties of competing potential models. By systematically sampling the potential energy surface of crystalline tetracene, we assess how the number, energy and structure of its minima are modified by switching on (or off) the Coulombic interactions. The increased complexity of the Coulombic potential leads to a more "rugged" potential energy surface with a larger number of minima, but the effect is not large. In fact, we find a subset of minima stable only in presence of the Coulombic interactions, a smaller subset stable only in their absence, and a large majority stable in both cases. Among these, there is a very good, but not perfect, correlation between the energies and the structures computed with and without the electrostatic interactions. Although electrostatic interactions play a role even in a rigid nonpolar molecule such as tetracene, they are not as crucial as often believed, because altering the electrostatic model (or switching it off completely) leads, in most cases, to equivalent results.     

Polymorphism and Phonon Dynamics of α‐Quaterthiophene

Two 4T: Low‐frequency micro‐Raman spectroscopy coupled with lattice dynamics calculations is an invaluable tool for investigating polymorphism in organic semiconductors. The Raman spectra of the low‐temperature (LT) and high‐temperature (HT) polymorphs of α‐quaterthiophene (4T) are presented and interpreted (see picture). Raman mapping is applied to investigate the phase purity.

     

Limit of hanger linearity in suspension footbridge dynamics: A new section model

The mechanical behaviour of suspension bridges is characterised by nonlinearities due to the main cables geometric effects and to the inability of the hangers to sustain compressive loads. The nonlinear effects due to hanger slackening are expected to increase in suspension footbridges due to lightweight decks, that is, low dead to live load ratio, and to shallow plate-girder decks with very low flexural and torsional stiffness. In this paper a new section model is proposed to study the limit of hanger linearity in lightweight suspension footbridges. The model is inspired to a four degrees-of-freedom model already proposed in the literature, but is expressed with a new formalism that allows some interesting properties to be outlined. Specifically, the expression of a particular frequency, herein called relative antiresonance frequency, as a function of the model generalised properties is derived: if the system is loaded with a harmonic force having that frequency, the linear behaviour of the hangers is assured for every value of the force amplitude. The proposed section model is applied to a footbridge benchmark subject to the pedestrian harmonic load and results are compared with those obtained through a nonlinear dynamic analysis on a 3D Finite Element model of the bridge.     

Long-distance entanglement in spin systems

Most quantum system with short-ranged interactions show a fast decay of entanglement with the distance. In this Letter, we focus on the peculiarity of some systems to distribute entanglement between distant parties. Even in realistic models, like the spin-1 Heisenberg chain, sizable entanglement is present between arbitrarily distant particles. We show that long-distance entanglement appears for values of the microscopic parameters which do not coincide with known quantum critical points, hence signaling a transition detected only by genuine quantum correlations.     

Computational study on the interaction of water with 2- and 3-hydroxypyridine and the corresponding pyridones

SCF –MO –LCAO ab-initio computations were carried out for the four tautomers 2-pyridone, 2-hydroxypyridine, 3-pyridone, and 3-hydroxypyridine interacting with a water molecule placed at different positions and orientations around each of them. The computed interaction energies were fitted by an analytical potential consisting of a 6–12 Lennard-Jones term plus a Coulombic one. The root-mean-square deviation of the fit is 2.5 kJ/mol. We report isoenergy contour maps for some important cross sections and obtain a qualitative trend of the solvation entropy, in agreement with available experimental data. The obtained potentials were used for Monte Carlo simulation of four clusters consisting of a tautomer molecule as solute and 50 water molecules, at 300 K. The problem of the transferability of fitting constants is also examined.