Density functional theory and DFT+U study of transition metal porphines adsorbed on Au(111) surfaces and effects of applied electric fields

We apply Density Functional Theory (DFT) and the DFT+U technique to study the adsorption of transition metal porphine molecules on atomistically flat Au(111) surfaces. DFT calculations using the Perdew-Burke-Ernzerhof (PBE) exchange correlation functional correctly predict the palladium porphine (PdP) low-spin ground state. PdP is found to adsorb preferentially on gold in a flat geometry, not in an edgewise geometry, in qualitative agreement with experiments on substituted porphyrins. It exhibits no covalent bonding to Au(111), and the binding energy is a small fraction of an eV. The DFT+U technique, parameterized to B3LYP predicted spin state ordering of the Mn d-electrons, is found to be crucial for reproducing the correct magnetic moment and geometry of the isolated manganese porphine (MnP) molecule. Adsorption of Mn(II)P on Au(111) substantially alters the Mn ion spin state. Its interaction with the gold substrate is stronger and more site-specific than PdP. The binding can be partially reversed by applying an electric potential, which leads to significant changes in the electronic and magnetic properties of adsorbed MnP, and ~ 0.1 Angstrom, changes in the Mn-nitrogen distances within the porphine macrocycle. We conjecture that this DFT+U approach may be a useful general method for modeling first row transition metal ion complexes in a condensed-matter setting.Comment: 14 pages, 6 figure

Large scale numerical investigation of excited states in poly(phenylene)

A density matrix renormalisation group scheme is developed, allowing for the first time essentially exact numerical solutions for the important excited states of a realistic semi-empirical model for oligo-phenylenes. By monitoring the evolution of the energies with chain length and comparing them to the experimental absorption peaks of oligomers and thin films, we assign the four characteristic absorption peaks of phenyl-based polymers. We also determine the position and nature of the nonlinear optical states in this model.Comment: RevTeX, 10 pages, 4 eps figures included using eps

Ultrafast optical nonlinearity in quasi-one-dimensional Mott-insulator Sr2CuO3{\rm Sr_2CuO_3}

We report strong instantaneous photoinduced absorption (PA) in the quasi-one-dimensional Mott insulator ${\rm Sr_2CuO_3}$ in the IR spectral region. The observed PA is to an even-parity two-photon state that occurs immediately above the absorption edge. Theoretical calculations based on a two-band extended Hubbard model explains the experimental features and indicates that the strong two-photon absorption is due to a very large dipole-coupling between nearly degenerate one- and two-photon states. Room temperature picosecond recovery of the optical transparency suggests the strong potential of ${\rm Sr_2CuO_3}$ for all-optical switching.Comment: 10 pages, 4 figure

A theoretical investigation of the low lying electronic structure of poly(p-phenylene vinylene)

The two-state molecular orbital model of the one-dimensional phenyl-based semiconductors is applied to poly(p-phenylene vinylene). The energies of the low-lying excited states are calculated using the density matrix renormalization group method. Calculations of both the exciton size and the charge gap show that there are both Bu and Ag excitonic levels below the band threshold. The energy of the 1Bu exciton extrapolates to 2.60 eV in the limit of infinite polymers, while the energy of the 2Ag exciton extrapolates to 2.94 eV. The calculated binding energy of the 1Bu exciton is 0.9 eV for a 13 phenylene unit chain and 0.6 eV for an infinite polymer. This is expected to decrease due to solvation effects. The lowest triplet state is calculated to be at ca. 1.6 eV, with the triplet-triplet gap being ca. 1.6 eV. A comparison between theory, and two-photon absorption and electroabsorption is made, leading to a consistent picture of the essential states responsible for most of the third-order nonlinear optical properties. An interpretation of the experimental nonlinear optical spectroscopies suggests an energy difference of ca. 0.4 eV between the vertical energy and ca. 0.8 eV between the relaxed energy, of the 1Bu exciton and the band gap, respectively.Comment: LaTeX, 19 pages, 7 eps figures included using epsf. To appear in Physical Review B, 199

Excitonic Strings in one dimensional organic compounds

Important questions concern the existence of excitonic strings in organic compounds and their signatures in the photophysics of these systems. A model in terms of Hard Core Bosons is proposed to study this problem in one dimension. Mainly the cases with two and three particles are studied for finite and infinite lattices, where analytical results are accessible. It is shown that if bi-excitonic states exist, three-excitonic and even, n-excitonic strings, at least in a certain range of parameters, will exist. Moreover, the behaviour of the transitions from one exciton to the biexciton is fully clarified. The results are in agreement with exact finite cluster diagonalizations of several model Hamiltonians.Comment: 36 pages, 4 eps figs. to appear in Phys. Rev.

Ab-initio calculation of the electronic and optical excitations in polythiophene: effects of intra- and interchain screening

We present an calculation of the electronic and optical excitations of an isolated polythiophene chain as well as of bulk polythiophene. We use the GW approximation for the electronic self-energy and include excitonic effects by solving the electron-hole Bethe-Salpeter equation. The inclusion of interchain screening in the case of bulk polythiophene drastically reduces both the quasi-particle band gap and the exciton binding energies, but the optical gap is hardly affected. This finding is relevant for conjugated polymers in general.Comment: 4 pages, 1 figur

Excitons in quasi-one dimensional organics: Strong correlation approximation

An exciton theory for quasi-one dimensional organic materials is developed in the framework of the Su-Schrieffer-Heeger Hamiltonian augmented by short range extended Hubbard interactions. Within a strong electron-electron correlation approximation, the exciton properties are extensively studied. Using scattering theory, we analytically obtain the exciton energy and wavefunction and derive a criterion for the existence of a $B_u$ exciton. We also systematically investigate the effect of impurities on the coherent motion of an exciton. The coherence is measured by a suitably defined electron-hole correlation function. It is shown that, for impurities with an on-site potential, a crossover behavior will occur if the impurity strength is comparable to the bandwidth of the exciton, corresponding to exciton localization. For a charged impurity with a spatially extended potential, in addition to localization the exciton will dissociate into an uncorrelated electron-hole pair when the impurity is sufficiently strong to overcome the Coulomb interaction which binds the electron-hole pair. Interchain coupling effects are also discussed by considering two polymer chains coupled through nearest-neighbor interchain hopping $t_{\perp}$ and interchain Coulomb interaction $V_{\perp}$. Within the $t$ matrix scattering formalism, for every center-of-mass momentum, we find two poles determined only by $V_{\perp}$, which correspond to the interchain excitons. Finally, the exciton state is used to study the charge transfer from a polymer chain to an adjacent dopant molecule.Comment: 24 pages, 23 eps figures, pdf file of the paper availabl

Polar and hydrogen-bonding effects of alcohols on the emission spectrum of styrene-triethylamine system

The emission spectra of styrene (ST)-triethylamine (TEA) systems were measured under steady-state illumination conditions in some THF-protic solvent mixtures. The fluorescence spectrum of the ST-TEA system in THF consists of two bands (band A at 304 nm (fluorescence of ST) and band B at 460 nm (emission from an exciplex)). The intensity of band A increased and that of band B decreased with increasing amounts of protic solvents in THF-protic solvent mixtures. The increase in the intensity of band A was explained by the decrease in the concentration of free amine owing to the hydrogen-bonding interaction (or protonation) between TEA and protic solvents. The decrease in the intensity of band B was considered to be caused by the decrease in the concentration of free amine on the addition of protic solvents and the enhanced conversion of the exciplex to an ion pair with increasing solvent polarity. The polar effect was expressed as a function of the relative permittivity of the solution.</p

Ab-initio prediction of the electronic and optical excitations in polythiophene: isolated chains versus bulk polymer

We calculate the electronic and optical excitations of polythiophene using the GW approximation for the electronic self-energy, and include excitonic effects by solving the electron-hole Bethe-Salpeter equation. Two different situations are studied: excitations on isolated chains and excitations on chains in crystalline polythiophene. The dielectric tensor for the crystalline situation is obtained by modeling the polymer chains as polarizable line objects, with a long-wavelength polarizability tensor obtained from the ab-initio polarizability function of the isolated chain. With this model dielectric tensor we construct a screened interaction for the crystalline case, including both intra- and interchain screening. In the crystalline situation both the quasi-particle band gap and the exciton binding energies are drastically reduced in comparison with the isolated chain. However, the optical gap is hardly affected. We expect this result to be relevant for conjugated polymers in general.Comment: 15 pages including 4 figures; to appear in Phys. Rev. B, 6/15/200