Mesoscopic modelling of bipolar charge evolution in CN-PPV LEDs

Since various chances are possible in the molecular structure of the repeat unit, substituted poly(para-phenylenevinylene) (PPV) has ben used as active component in light-emitting diodes (LEDs) to obtain light emission in a wide range of colours.A major aspect determining device performance is the competition between current flow, trapping and recombination within the polymer layer. By suitable Monte Carlo calculations, we have performed computer experiments in which bipolar charge carriers are injected at constant rate in polymer networks made of cyano-substituted PPV chains with variable length and orientation. The intra-molecular electronic properties used in these simulations were calculated by a quantum molecular dynamics method. In order to assess the influence of cyano-substitution on the properties of single-layer PPV LEDs, we have focused our attention on bipolar charge evolution in time. Specifically addressed are the differences in electric field strength needed for intra-molecular charge mobility of electrons and holes and their consequences at mesoscopic scale. (C) 2004 Elsevier B.V. All rights reserved

Bridge Hopping on Conducting Polymers in Solution

Configurational fluctuations of conducting polymers in solution can bring into proximity monomers which are distant from each other along the backbone. Electrons can hop between these monomers across the "bridges" so formed. We show how this can lead to (i) a collapse transition for metallic polymers, and (ii) to the observed dramatic efficiency of acceptor molecules for quenching fluorescence in semiconducting polymers.Comment: RevTeX 12 pages + 2 Postscript figure

Polaron Self-localization in White-light Emitting Hybrid Perovskites

Two-dimensional (2D) perovskites with general formula $APbX_4$ are attracting increasing interest as solution processable, white-light emissive materials. Recent studies have shown that their broadband emission is related to the formation of intra-gap color centers; however, the nature and dynamics of the emissive species have remained elusive. Here we show that the broadband photoluminescence of the 2D perovskites $(EDBE)PbCl_4$ and $(EDBE)PbBr_4$ stems from the localization of small polarons within the lattice distortion field. Using a combination of spectroscopic techniques and first-principles calculations, we infer the formation of ${Pb_2}^{3+}$, $Pb^{3+}$, and ${X_2}^-$ (where X=Cl or Br) species confined within the inorganic perovskite framework. Due to strong Coulombic interactions, these species retain their original excitonic character and form self-trapped polaron-excitons acting as radiative color centers. These findings are expected to be applicable to a broad class of white-light emitting perovskites with large polaron relaxation energy.Comment: 34 pages, 15 figures, 3 table

The coupled electronic oscillators vs the sum-over-states pictures for the optical response of octatetraene

A coupled electronic oscillator (CEO) analysis of the third harmonic generation (THG) spectrum for octatetraene is presented. The dominant oscillators and their couplings are identified using tree diagrams. The correspondence between the dominant oscillators in the CEO picture and the relevant excited states in the sum-over-states (SOS) description is demonstrated. The important channels in the SOS are related to the dominant oscillator pathways in the CEO picture. © 1996 American Institute of Physics.published_or_final_versio

Breakdown of the mirror image symmetry in the optical absorption/emission spectra of oligo(para-phenylene)s

The absorption and emission spectra of most luminescent, pi-conjugated, organic molecules are the mirror image of each other. In some cases, however, this symmetry is severely broken. In the present work, the asymmetry between the absorption and fluorescence spectra in molecular systems consisting of para-linked phenyl rings is studied. The vibronic structure of the emission and absorption bands is calculated from ab-initio quantum chemical methods and a subsequent, rigorous Franck-Condon treatment. Good agreement with experiment is achieved. A clear relation can be established between the strongly anharmonic double-well potential for the phenylene ring librations around the long molecular axis and the observed deviation from the mirror image symmetry. Consequences for related compounds and temperature dependent optical measurements are also discussed.Comment: 12 pages, 13 Figure

Dynamical nonlinear optical coefficients from the symmetrized density-matrix renormalization-group method

We extend the symmetrized density-matrix renormalization-group method to compute the dynamic nonlinear optical coefficients for long chains. By computing correction vectors in the appropriate symmetry subspace, we obtain the dynamic polarizabilities, αij(ω), and third-order polarizabilities γijkl(ω,ω,ω) of the Hubbard and "U-V" chains in an all transpolyacetylene geometry, with and without dimerization. We rationalize the behavior of α̅ and γ̅ on the basis of the low-lying excitation gaps in the system. This is the first study of the dynamics of a fermionic system within the DMRG framework

A multimode analysis of the gas-phase photoelectron spectra in oligoacenes

© 2004 American Institute of Physics. The electronic version of this article is the complete one and can be found at: http://dx.doi.org/10.1063/1.1687675DOI: 10.1063/1.1687675We present a multimode vibrational analysis of the gas-phase ultraviolet photoelectron spectra of the first ionization in anthracene, tetracene, and pentacene, using electron-vibration constants computed at the density functional theory level. The first ionization of each molecule exhibits a high-frequency vibronic structure; it is shown that this regularly spaced feature is actually the consequence of the collective action of several vibrational modes rather than the result of the interaction with a single mode. We interpret this feature in terms of the missing mode effect. We also discuss the vibronic coupling constants and relaxation energies obtained from the fit of the photoelectron spectra with the linear vibronic model

To bend or not to bend – are heteroatom interactions within conjugated molecules effective in dictating conformation and planarity?

We consider the roles of heteroatoms (mainly nitrogen, the halogens and the chalcogens) in dictating the conformation of linear conjugated molecules and polymers through non-covalent intramolecular interactions. Whilst hydrogen bonding is a competitive and sometimes more influential interaction, we provide unambiguous evidence that heteroatoms are able to determine the conformation of such materials with reasonable predictability