Excitonic Funneling in Extended Dendrimers with Non-Linear and Random Potentials

The mean first passage time (MFPT) for photoexcitations diffusion in a funneling potential of artificial tree-like light-harvesting antennae (phenylacetylene dendrimers with generation-dependent segment lengths) is computed. Effects of the non-linearity of the realistic funneling potential and slow random solvent fluctuations considerably slow down the center-bound diffusion beyond a temperature-dependent optimal size. Diffusion on a disordered Cayley tree with a linear potential is investigated analytically. At low temperatures we predict a phase in which the MFPT is dominated by a few paths.Comment: 4 pages, 4 figures, To be published in Phys. Rev. Let

Disorder and Funneling Effects on Exciton Migration in Tree-Like Dendrimers

The center-bound excitonic diffusion on dendrimers subjected to several types of non-homogeneous funneling potentials, is considered. We first study the mean-first passage time (MFPT) for diffusion in a linear potential with different types of correlated and uncorrelated random perturbations. Increasing the funneling force, there is a transition from a phase in which the MFPT grows exponentially with the number of generations $g$, to one in which it does so linearly. Overall the disorder slows down the diffusion, but the effect is much more pronounced in the exponential compared to the linear phase. When the disorder gives rise to uncorrelated random forces there is, in addition, a transition as the temperature $T$ is lowered. This is a transition from a high-$T$ regime in which all paths contribute to the MFPT to a low-$T$ regime in which only a few of them do. We further explore the funneling within a realistic non-linear potential for extended dendrimers in which the dependence of the lowest excitonic energy level on the segment length was derived using the Time-Dependent Hatree-Fock approximation. Under this potential the MFPT grows initially linearly with $g$ but crosses-over, beyond a molecular-specific and $T$-dependent optimal size, to an exponential increase. Finally we consider geometrical disorder in the form of a small concentration of long connections as in the {\it small world} model. Beyond a critical concentration of connections the MFPT decreases significantly and it changes to a power-law or to a logarithmic scaling with $g$, depending on the strength of the funneling force.Comment: 13 pages, 9 figure

Quasiparticle Density-Matrix Representation of Nonlinear TDDFT Response Functions

The time-dependent density functional (TDDFT) equations may be written either for the Kohn-Sham orbitals in Hilbert space or for the single electron density matrix in Liouville space. A collective-oscillator, quasiparticle, representation of the density response of many-electron systems which explicitly reveals the relevant electronic coherence sizes is developed using the Liouville space representation of adiabatic TDDFT. Closed expressions for the nonlinear density-density response are derived, eliminating the need to solve nonlinear integral equations, as required in the Hilbert space formulation of the response.Comment: 24 page

Current Profiles of Molecular Nanowires; DFT Green Function Representation

The Liouville-space Green function formalism is used to compute the current density profile across a single molecule attached to electrodes. Time ordering is maintained in real, physical, time, avoiding the use of artificial time loops and backward propagations. Closed expressions for molecular currents, which only require DFT calculations for the isolated molecule, are derived to fourth order in the molecule/electrode coupling.Comment: 21 page

Analytical solutions to the third-harmonic generation in trans-polyacetylene: Application of dipole-dipole correlation on the single electron models

The analytical solutions for the third-harmonic generation (THG) on infinite chains in both Su-Shrieffer-Heeger (SSH) and Takayama-Lin-Liu-Maki (TLM) models of trans-polyacetylene are obtained through the scheme of dipole-dipole ($DD$) correlation. They are not equivalent to the results obtained through static current-current ($J_0J_0$) correlation or under polarization operator $\hat{P}$. The van Hove singularity disappears exactly in the analytical forms, showing that the experimentally observed two-photon absorption peak (TPA) in THG may not be directly explained by the single electron models.Comment: 10 pages, 4 figures, submitted to Phys. Rev.

Optoelectronic Properties of Carbon Nanorings: Excitonic Effects from Time-Dependent Density Functional Theory

The electronic structure and size-scaling of optoelectronic properties in cycloparaphenylene carbon nanorings are investigated using time-dependent density functional theory (TDDFT). The TDDFT calculations on these molecular nanostructures indicate that the lowest excitation energy surprisingly becomes larger as the carbon nanoring size is increased, in contradiction with typical quantum confinement effects. In order to understand their unusual electronic properties, I performed an extensive investigation of excitonic effects by analyzing electron-hole transition density matrices and exciton binding energies as a function of size in these nanoring systems. The transition density matrices allow a global view of electronic coherence during an electronic excitation, and the exciton binding energies give a quantitative measure of electron-hole interaction energies in the nanorings. Based on overall trends in exciton binding energies and their spatial delocalization, I find that excitonic effects play a vital role in understanding the unique photoinduced dynamics in these carbon nanoring systems.Comment: Accepted by the Journal of Physical Chemistry

Structure, Photophysics and the Order-Disorder Transition to the Beta Phase in Poly(9,9-(di -n,n-octyl)fluorene)

X-ray diffraction, UV-vis absorption and photoluminescence (PL) spectroscopy have been used to study the well-known order-disorder transition (ODT) to the beta phase in poly(9,9-(di n,n-octyl)fluorene)) (PF8) thin film samples through combination of time-dependent and temperature-dependent measurements. The ODT is well described by a simple Avrami picture of one-dimensional nucleation and growth but crystallization, on cooling, proceeds only after molecular-level conformational relaxation to the so called beta phase. Rapid thermal quenching is employed for PF8 studies of pure alpha phase samples while extended low-temperature annealing is used for improved beta phase formation. Low temperature PL studies reveal sharp Franck-Condon type emission bands and, in the beta phase, two distinguishable vibronic sub-bands with energies of approximately 199 and 158 meV at 25 K. This improved molecular level structural order leads to a more complete analysis of the higher-order vibronic bands. A net Huang-Rhys coupling parameter of just under 0.7 is typically observed but the relative contributions by the two distinguishable vibronic sub-bands exhibit an anomalous temperature dependence. The PL studies also identify strongly correlated behavior between the relative beta phase 0-0 PL peak position and peak width. This relationship is modeled under the assumption that emission represents excitons in thermodynamic equilibrium from states at the bottom of a quasi-one-dimensional exciton band. The crystalline phase, as observed in annealed thin-film samples, has scattering peaks which are incompatible with a simple hexagonal packing of the PF8 chains.Comment: Submitted to PRB, 12 files; 1 tex, 1 bbl, 10 eps figure

The Reform of Employee Compensation in China’s Industrial Enterprises

Although employee compensation reform in Chinese industrial sector has been discussed in the literature, the real changes in compensation system and pay practices have received insufficient attention and warrant further examination. This paper briefly reviews the pre- and post-reform compensation system, and reports the results of a survey of pay practices in the four major types of industrial enterprises in China. The research findings indicate that the type of enterprise ownership has little influence on general compensation practices, adoption of profit-sharing plans, and subsidy and allowance packages. In general, pay is linked more to individual performance and has become an important incentive to Chinese employees. However, differences are found across the enterprise types with regard to performance-related pay. Current pay practices are positively correlated to overall effectiveness of the enterprise

Excitons in a Photosynthetic Light-Harvesting System: A Combined Molecular Dynamics/Quantum Chemistry and Polaron Model Study

The dynamics of pigment-pigment and pigment-protein interactions in light-harvesting complexes is studied with a novel approach which combines molecular dynamics (MD) simulations with quantum chemistry (QC) calculations. The MD simulations of an LH-II complex, solvated and embedded in a lipid bilayer at physiological conditions (with total system size of 87,055 atoms) revealed a pathway of a water molecule into the B800 binding site, as well as increased dimerization within the B850 BChl ring, as compared to the dimerization found for the crystal structure. The fluctuations of pigment (B850 BChl) excitation energies, as a function of time, were determined via ab initio QC calculations based on the geometries that emerged from the MD simulations. From the results of these calculations we constructed a time-dependent Hamiltonian of the B850 exciton system from which we determined the linear absorption spectrum. Finally, a polaron model is introduced to describe quantum mechanically both the excitonic and vibrational (phonon) degrees of freedom. The exciton-phonon coupling that enters into the polaron model, and the corresponding phonon spectral function are derived from the MD/QC simulations. It is demonstrated that, in the framework of the polaron model, the absorption spectrum of the B850 excitons can be calculated from the autocorrelation function of the excitation energies of individual BChls, which is readily available from the combined MD/QC simulations. The obtained result is in good agreement with the experimentally measured absorption spectrum.Comment: REVTeX3.1, 23 pages, 13 (EPS) figures included. A high quality PDF file of the paper is available at http://www.ks.uiuc.edu/Publications/Papers/PDF/DAMJ2001/DAMJ2001.pd