Homologous classes of Polycyclic Aromatic Hydrocarbons (PAHs) in their crystalline state are among the most promising materials for organic opto-electronics. Following previous works on oligoacenes we present a systematic comparative study of the electronic, optical, and transport properties of oligoacenes, phenacenes, circumacenes, and oligorylenes. Using density functional theory (DFT) and timedependent DFT we computed: (i) electron affinities and first ionization energies; (ii) quasiparticle correction to the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap; (iii) molecular reorganization energies; (iv) electronic absorption spectra of neutral and ±1 charged systems. The excitonic effects are estimated by comparing the optical gap and the quasiparticle corrected HOMO-LUMO energy gap. For each molecular property computed, general trends as a function of molecular size and charge state are discussed. Overall, we find that circumacenes have the best transport properties, displaying a steeper decrease of the molecular reorganization energy at increasing sizes, while oligorylenes are much more efficient in absorbing low-energy photons in comparison to the other classes.

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We present a systematic theoretical study of the five smallest oligoacenes (naphthalene, anthracene, tetracene, pentacene, and hexacene) in their anionic, neutral, cationic, and dicationic charge states. We used density functional theory (DFT) to obtain the ground-state optimised geometries, and time-dependent DFT (TD-DFT) to evaluate the electronic absorption spectra. Total-energy differences enabled us to evaluate the electron affinities and first and second ionisation energies, the quasiparticle correction to the HOMO-LUMO energy gap and an estimate of the excitonic effects in the neutral molecules. Electronic absorption spectra have been computed by combining two different implementations of TD-DFT: the frequency-space method to study general trends as a function of charge-state and molecular size for the lowest-lying in-plane long-polarised and short-polarised π → π ⋆ electronic transitions, and the real-time propagation scheme to obtain the whole photo-absorption cross-section up to the far-UV. Doubly-ionised PAHs are found to display strong electronic transitions of π → π ⋆ character in the near-IR, visible, and near-UV spectral ranges, like their singly-charged counterparts. While, as expected, the broad plasmon-like structure with its maximum at about 17-18 eV is relatively insensitive to the charge-state of the molecule, a systematic decrease with increasing positive charge of the absorption cross-section between ∼6 and ∼12 eV is observed for each member of the class.

Exact solutions are presented to the steady-state coupled-mode equations that govern the nonlinear parametric interaction of a central-frequency wave with a pair of upshifted and downshifted sidebands in isotropic single mode optical fibers. This solution accounts for pump depletion as well for as a possible phase mismatch among the waves. The existence is predicted of eigensolutions propagating unchanged along the fiber, which may be either spatially stable or spatially unstable, depending on the total power and the propagation-constant mismatch. The presence of spatially unstable eigensolutions dramatically affects the power exchange among the three waves. The physical implications of this instability for the frequency-conversion process, as well as its potential application to all-optical switching, are discussed

We present a model for the dielectric function of semiconductors. It has been tested successfully for\ud Si, Ge, GaAs, and ZnSe. In conjunction with the single plasmon-pole approximation it yields plasmonenergy\ud dispersions in fair agreement with experiments. It allows one, moreover, to deduce an analytical\ud expression for the Coulomb-hole part of the static self-energy operator

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Abstract. We present theoretical electron affinities, calculated as total energy differences, for a large sample of polycyclic aromatic hydrocarbons (PAHs), ranging in size from azulene (C 10 H 8 ) to dicoronylene (C 48 H 20 ). For 20 out of 22 molecules under study we obtained electron affinity values in the range 0.4-2.0 eV, showing them to be able to accept an additional electron in their LUMO π orbital. For the mono-anions we computed the absolute photo-absorption cross-sections up to the vacuum ultraviolet (VUV) using an implementation in real time and real space of the Time-Dependent Density Functional Theory (TD-DFT), an approach which has already been proven to yield accurate results for neutral and cationic PAHs. Comparison with available experimental data hints that this is the case for mono-anions as well. We find that PAH anions, like their parent molecules and the corresponding cations, display strong π * ← π electronic transitions in the UV. The present results provide a quantitative foundation to estimate the fraction of specific PAHs which can be singly negatively charged in various interstellar environments, to simulate their photophysics in detail and to evaluate their contribution to the interstellar extinction curve.