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

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

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

Electrochemical synthesis of new electroactive polymers from dithienylene-vinylene derivatives

peer reviewedHighly conjugated thiophene derivatives, based on thienylene-vinylene and thieneylene-vinylene-phenylene units, have been synthesized in order to examine: (i) the effect of such regular conjugated monomer structures on the polymerization; (ii) the optical and electrochemical properties of the corresponding conjugated polymers. The all-trans monomers have been prepared by a Wittig reaction and the polymers have then been synthesized electrochemically. The polymers are electrochromic and can be reversibly doped both oxidatively and reductively. Their electrochemical behavior and optical properties have been analysed on the basis of quantum-chemical calculations

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

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

Impact of interfacial molecular orientation on radiative recombination and charge generation efficiency.

A long standing question in organic electronics concerns the effects of molecular orientation at donor/acceptor heterojunctions. Given a well-controlled donor/acceptor bilayer system, we uncover the genuine effects of molecular orientation on charge generation and recombination. These effects are studied through the point of view of photovoltaics-however, the results have important implications on the operation of all optoelectronic devices with donor/acceptor interfaces, such as light emitting diodes and photodetectors. Our findings can be summarized by two points. First, devices with donor molecules face-on to the acceptor interface have a higher charge transfer state energy and less non-radiative recombination, resulting in larger open-circuit voltages and higher radiative efficiencies. Second, devices with donor molecules edge-on to the acceptor interface are more efficient at charge generation, attributed to smaller electronic coupling between the charge transfer states and the ground state, and lower activation energy for charge generation.Molecular orientation profoundly affects the performance of donor-acceptor heterojunctions, whilst it has remained challenging to investigate the detail. Using a controllable interface, Ran et al. show that the edge-on geometries improve charge generation at the cost of non-radiative recombination loss

Tailoring on-surface molecular reactions and assembly through hydrogen-modified synthesis: From triarylamine monomer to 2D covalent organic framework

Relative to conventional wet-chemical synthesis techniques, on-surface synthesis of organic networks in ultrahigh vacuum has few control parameters. The molecular deposition rate and substrate temperature are typically the only synthesis variables to be adjusted dynamically. Here we demonstrate that reducing conditions in the vacuum environment can be created and controlled without dedicated sources -- relying only on backfilled hydrogen gas and ion gauge filaments -- and can dramatically influence the Ullmann-like on-surface reaction used for synthesizing two-dimensional covalent organic frameworks (2D COFs). Using tribromo dimethylmethylene-bridged triphenylamine ((Br$_3$)DTPA) as monomer precursors, we find that atomic hydrogen blocks aryl-aryl bond formation. Control of the relative monomer and hydrogen fluxes is used to produce large islands of self-assembled monomers, dimers, or macrocycle hexamers. On-surface synthesis of these oligomers, from a single precursor, circumvents potential challenges with protracted wet-chemical synthesis or low precursor volatility for large molecules. Using scanning tunneling microscopy and spectroscopy (STM/STS), we show that changes in the electronic states through this oligomer sequence provide an insightful view of the 2D-COF (synthesized in the absence of atomic hydrogen) as the endpoint in an evolution of electronic structures from the monomer

Mode-selective vibrational control of charge transport in ππ-conjugated molecular materials

The soft character of organic materials leads to strong coupling between molecular nuclear and electronic dynamics. This coupling opens the way to control charge transport in organic electronic devices by inducing molecular vibrational motions. However, despite encouraging theoretical predictions, experimental realization of such control has remained elusive. Here we demonstrate experimentally that photoconductivity in a model organic optoelectronic device can be controlled by the selective excitation of molecular vibrations. Using an ultrafast infrared laser source to create a coherent superposition of vibrational motions in a pentacene/C60 photoresistor, we observe that excitation of certain modes in the 1500-1700 cm$^{-1}$ region leads to photocurrent enhancement. Excited vibrations affect predominantly trapped carriers. The effect depends on the nature of the vibration and its mode-specific character can be well described by the vibrational modulation of intermolecular electronic couplings. Vibrational control thus presents a new tool for studying electron-phonon coupling and charge dynamics in (bio)molecular materials.This work was supported by the Netherlands Organization for Scientific Research (NWO) through the ‘Stichting voor Fundamenteel Onderzoek der Materie’ (FOM) research programme. A.A.B. also acknowledges a VENI grant from the NWO. A.A.B. is currently a Royal Society University Research Fellow. This project has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (grant agreement No 639750). R.L. acknowledges a Marie Curie IE Fellowship from the EU, held at the Weizmann Institute (FP7-PEOPLE-2011-IEF no. 29866). X.Y. thanks the Council for Higher Education (Israel) for a PBC programme postdoctoral research fellowship. V.C. thanks support from the Office of Naval Research and MURI Center on Advanced Molecular Photovoltaics, award No. N00014-14-1-0580. J.L.B. acknowledges support by competitive research funding from King Abdullah University of Science and Technology (KAUST) and by ONR Global, Grant N62909-15-1-2003. D.C. thanks the Israel Science Foundation Centre of Excellence program, the Grand Centre for Sensors and Security and the Schmidt Minerva Centre for Supramolecular Architecture for partial support. D.C. holds the Sylvia and Rowland Schaefer Chair in Energy Research.This is the final published version. It first appeared at http://dx.doi.org/10.1038/ncomms888