Electron Correlations and Two-Photon States in Polycyclic Aromatic Hydrocarbon Molecules: A Peculiar Role of Geometry

We present numerical studies of one- and two-photon excited states ordering in a number of polycyclic aromatic hydrocarbon molecules: coronene, hexa-peri-hexabenzocoronene and circumcoronene, all possessing $D_{6h}$ point group symmetry versus ovalene with $D_{2h}$ symmetry, within the Pariser-Parr-Pople model of interacting $\pi$-electrons. The calculated energies of the two-photon states as well as their relative two-photon absorption cross-sections within the interacting model are qualitatively different from single-particle descriptions. More remarkably, a peculiar role of molecular geometry is found. The consequence of electron correlations is far stronger for ovalene, where the lowest spin-singlet two-photon state is a quantum superposition of pairs of lowest spin triplet states, as in the linear polyenes. The same is not true for $D_{6h}$ group hydrocarbons. Our work indicates significant covalent character, in valence bond language, of the ground state, the lowest spin triplet state and a few of the lowest two-photon states in $D_{2h}$ ovalene but not in those with $D_{6h}$ symmetry.Comment: 11 pages, 3 figures, 3 table

Theory of interfacial charge-transfer complex photophysics in π\pi-conjugated polymer-fullerene blends

We present a theory of the electronic structure and photophysics of 1:1 blends of derivatives of polyparaphenylenevinylene and fullerenes. Within the same Coulomb-correlated Hamiltonian applied previously to interacting chains of single-component $\pi$-conjugated polymers, we find an exciplex state that occurs below the polymer's optical exciton. Weak absorption from the ground state occurs to the exciplex. We explain transient photoinduced absorptions in the blend, observed for both above-gap and below-gap photoexcitations, within our theory. Photoinduced absorptions for above-gap photoexcitation are from the optical exciton as well as the exciplex, while for below-gap photoexcitation induced absorptions are from the exciplex alone. In neither case are free polarons generated in the time scale of the experiment. Importantly, the photophysics of films of single-component $\pi$-conjugated polymers and blends can both be understood by extending Mulliken's theory of ground-state charge transfer to the case of excited-state charge transfer.Comment: 9 pages, 8 figure

Subgap Two-Photon States in Polycyclic Aromatic Hydrocarbons: Evidence for Strong Electron Correlations

Strong electron correlation effects in the photophysics of quasi-one-dimensional $\pi$-conjugated organic systems such as polyenes, polyacetylenes, polydiacetylenes, etc., have been extensively studied. Far less is known on correlation effects in two-dimensional $\pi$-conjugated systems. Here we present theoretical and experimental evidence for moderate repulsive electron-electron interactions in a number of finite polycyclic aromatic hydrocarbon molecules with $D_{6h}$ symmetry. We show that the excited state orderings in these molecules are reversed relative to that expected within one-electron and mean-field theories. Our results reflect similarities as well as differences in the role and magnitude of electron correlation effects in these two-dimensional molecules compared to those in polyenes.Comment: 11 pages, 5 figures, 2 table

Dynamics of Impurity and Valence Bands in GaMnAs within the Dynamical Mean Field Approximation

We calculate the density-of-states and the spectral function of GaMnAs within the dynamical mean-field approximation. Our model includes the competing effects of the strong spin-orbit coupling on the J=3/2 GaAs hole bands and the exchange interaction between the magnetic ions and the itinerant holes. We study the quasi-particle and impurity bands in the paramagnetic and ferromagnetic phases for different values of impurity-hole coupling at the Mn doping of x=0.05. By analyzing the anisotropic angular distribution of the impurity band carriers at T=0, we conclude that the carrier polarization is optimal when the carriers move along the direction parallel to the average magnetization.Comment: 6 pages, 4 figure

Evidence for Excimer Photoexcitations in an Ordered {\pi}-Conjugated Polymer Film

We report pressure-dependent transient picosecond and continuous-wave photomodulation studies of disordered and ordered films of 2-methoxy-5-(2-ethylhexyloxy) poly(para-phenylenevinylene). Photoinduced absorption (PA) bands in the disordered film exhibit very weak pressure dependence and are assigned to intrachain excitons and polarons. In contrast, the ordered film exhibits two additional transient PA bands in the midinfrared that blueshift dramatically with pressure. Based on high-order configuration interaction calculations we ascribe the PA bands in the ordered film to excimers. Our work brings insight to the exciton binding energy in ordered films versus disordered films and solutions. The reduced exciton binding energy in ordered films is due to new energy states appearing below the continuum band threshold of the single strand.Comment: 5.5 pages, 5 figure

Fictive Impurity Models: an Alternative Formulation of the Cluster Dynamical Mean Field Method

"Cluster" extensions of the dynamical mean field method to include longer range correlations are discussed. It is argued that the clusters arising in these methods are naturally interpreted not as actual subunits of a physical lattice but as algorithms for computing coefficients in an orthogonal function expansion of the momentum dependence of the electronic self-energy. The difficulties with causality which have been found to plague cluster dynamical mean field methods are shown to be related to the "ringing" phenomenon familiar from Fourier analysis. The analogy is used to motivate proposals for simple filtering methods to circumvent them. The formalism is tested by comparison to low order perturbative calculations and self consistent solutions

k-dependent spectrum and optical conductivity near metal-insulator transition in multi-orbital Hubbard bands

We apply the dynamical mean field theory (DMFT) in the iterative perturbation theory(IPT) to doubly degenerate eg bands and triply degenerate tg bands on a simple cubic lattice and calculate the spectrum and optical conductivity in arbitrary electron occupation. The spectrum simultaneously shows the effects of multiplet structure and DMFT together with the electron ionization and affinity levels of different electron occupations, coherent peaks at the Fermi energy in the metallic phase and a gap at an integer filling of electrons for sufficiently large Coulomb U. We also calculate the critical value of the Coulomb U for degenerate orbitals.Comment: 8 pages, 6 figure

Triplet excitations in carbon nanostructures

We show that the energy differences between the lowest optical singlet exciton and the lowest triplet exciton in semiconducting single-walled carbon nanotubes with diameter $\sim 1$ nm and graphene nanoribbons with widths $\sim 2$ nm are an order of magnitude smaller than in the $\pi$-conjugated polymer poly(para-phenylenevinylene). Our calculated energy gaps between the singlet and triplet excitons are in excellent agreement with the measured values in three different nanotubes with diameters close to 1 nm. The spatial extent of the triplet exciton is nearly the same as that of the singlet exciton in wide nanotubes and nanoribbons, in contrast to that in $\pi$-conjugated polymers, in which the triplet exciton exhibits strong spatial confinement. Weakly confined behavior of the triplet state begins in nanoribbons with widths as narrow as 2.5 times the graphene unit lattice vector. We discuss possible consequences of the small singlet-triplet energy difference in the carbon nanostructures on device applications.Comment: 9 pages, 2 tables, 4 figure