Energy relaxation dynamics and universal scaling laws in organic light emitting diodes

Electron-hole (e-h) capture in luminescent conjugated polymers (LCPs) is modeled by the dissipative dynamics of a multilevel electronic system coupled to a phonon bath. Electroinjected e-h pairs are simulated by a mixed quantum state, which relaxes via phonon-driven internal conversions to low-lying charge-transfer (CT) and excitonic (XT) states. The underlying two-band polymer model reflects PPV and spans monoexcited configuration interaction singlets (S) and triplets (T), coupled to Franck-Condon active C=C stretches and ring-torsions. Focusing entirely upon long PPV chains, we consider the recombination kinetics of an initially separated CT pair. Our model calculations indicated that S and T recombination proceeds according to a branched, two-step mechanism dictated by near e-h symmetry. The initial relaxation occurs rapidly with nearly half of the population going into excitons ($S_{XT}$ or $T_{XT}$), while the remaining portion remains locked in metastable CT states. While formation rates of $S_{CT}$ and $T_{CT}$ are nearly equal, $S_{XT}$ is formed about twice as fast $T_{XT}$ in concurrence with experimental observations of these systems. Furthermore, breaking e-h symmetry suppresses the XT to CT branching ratio for triplets and opens a slow CT$\to$ XT conversion channel exclusively for singlets due to dipole-dipole interactions between geminate and non-geminate configurations. Finally, our calculations yield a remarkable linear relation between chain length and singlet/triplet branching ratio which can be explained in terms of the binding energies of the respective final excitonic states and the scaling of singlet-triplet energy gap with chain length.Comment: For IJQC-Sanibel Quantum Chemistry Symposium, 200

Car-Parrinello Molecular Dynamics on excited state surfaces

This paper describes a method to do ab initio molecular dynamics in electronically excited systems within the random phase approximation (RPA). Using a dynamical variational treatment of the RPA frequency, which corresponds to the electronic excitation energy of the system, we derive coupled equations of motion for the RPA amplitudes, the single particle orbitals, and the nuclear coordinates. These equations scale linearly with basis size and can be implemented with only a single holonomic constraint. Test calculations on a model two level system give exact agreement with analytical results. Furthermore, we examined the computational efficiency of the method by modeling the excited state dynamics of a one-dimensional polyene lattice. Our results indicate that the present method offers a considerable decrease in computational effort over a straight-forward configuration interaction (singles) plus gradient calculation performed at each nuclear configuration

Phonon-driven ultrafast exciton dissociation at donor-acceptor polymer heterojunctions

A quantum-dynamical analysis of phonon-driven exciton dissociation at polymer heterojunctions is presented, using a hierarchical electron-phonon model parameterized for three electronic states and 24 vibrational modes. Two interfering decay pathways are identified: a direct charge separation, and an indirect pathway via an intermediate bridge state. Both pathways depend critically on the dynamical interplay of high-frequency C=C stretch modes and low-frequency ring-torsional modes. The ultrafast, highly non-equilibrium dynamics is consistent with time-resolved spectroscopic observations

Presynaptic facilitation at the crayfish neuromuscular junction: Role of calcium-activated potassium conductance

Membrane potential was recorded intracellularly near presynaptic terminals of the excitor axon of the crayfish opener neuromuscular junction (NMJ), while transmitter release was recorded postsynaptically. This study focused on the effects of a presynaptic calcium-activated potassium conductance, gK(Ca), on the transmitter release evoked by single and paired depolarizing current pulses. Blocking gK(Ca) by adding tetraethylammonium ion (TEA; 5-20 mM) to a solution containing tetrodotoxin and aminopyridines caused the relation between presynaptic potential and transmitter release to steepen and shift to less depolarized potentials. When two depolarizing current pulses were applied at 20-ms intervals with gK(Ca) not blocked, the presynaptic voltage change to the second (test) pulse was inversely related to the amplitude of the first (conditioning) pulse. This effect of the conditioning prepulse on the response to the test pulse was eliminated by 20 mM TEA and by solutions containing 0 mM Ca2+/1 mM EGTA, suggesting that the reduction in the amplitude of the test pulse was due to activation of gK(Ca) by calcium remaining from the conditioning pulse. In the absence of TEA, facilitation of transmitter release evoked by a test pulse increased as the conditioning pulse grew from -40 to -20 mV, but then decreased with further increase in the conditioning depolarization. A similar nonmonotonic relationship between facilitation and the amplitude of the conditioning depolarization was reported in previous studies using extracellular recording, and interpreted as supporting an additional voltagedependent step in the activation of transmitter release. We suggest that this result was due instead to activation of a gK(Ca) by the conditioning depolarization, since facilitation of transmitter release increased monotonically with the amplitude of the conditioning depolarization, and the early time course of the decay of facilitation was prolonged when gK(Ca) was blocked. The different time courses for decay of the presynaptic potential (20 ms) and facilitation (> 50 ms) suggest either that residual free calcium does not account for facilitation at the crayfish NMJ or that the transmitter release mechanism has a markedly higher affinity or stoichiometry for internal free calcium than does g K(Ca). Finally, our data suggest that the calcium channels responsible for transmitter release at the crayfish NMJ are not of the L, N, or T type.This work was partially supported by NIAAA grant AA0776 to G. D. Bittner.Neuroscienc

Murine leukemia virus (MLV) replication monitored with fluorescent proteins

Background: Cancer gene therapy will benefit from vectors that are able to replicate in tumor tissue and cause a bystander effect. Replication-competent murine leukemia virus (MLV) has been described to have potential as cancer therapeutics, however, MLV infection does not cause a cytopathic effect in the infected cell and viral replication can only be studied by immunostaining or measurement of reverse transcriptase activity. Results: We inserted the coding sequences for green fluorescent protein (GFP) into the proline-rich region (PRR) of the ecotropic envelope protein (Env) and were able to fluorescently label MLV. This allowed us to directly monitor viral replication and attachment to target cells by flow cytometry. We used this method to study viral replication of recombinant MLVs and split viral genomes, which were generated by replacement of the MLV env gene with the red fluorescent protein (RFP) and separately cloning GFP-Env into a retroviral vector. Co-transfection of both plasmids into target cells resulted in the generation of semi-replicative vectors, and the two color labeling allowed to determine the distribution of the individual genomes in the target cells and was indicative for the occurrence of recombination events. Conclusions: Fluorescently labeled MLVs are excellent tools for the study of factors that influence viral replication and can be used to optimize MLV-based replication-competent viruses or vectors for gene therapy

Extremal transmission through a microwave photonic crystal and the observation of edge states in a rectangular Dirac billiard

This article presents experimental results on properties of waves propagating in an unbounded and a bounded photonic crystal consisting of metallic cylinders which are arranged in a triangular lattice. First, we present transmission measurements of plane waves traversing a photonic crystal. The experiments are performed in the vicinity of a Dirac point, i.e., an isolated conical singularity of the photonic band structure. There, the transmission shows a pseudodiffusive 1/L dependence, with $L$ being the thickness of the crystal, a phenomenon also observed in graphene. Second, eigenmode intensity distributions measured in a microwave analog of a relativistic Dirac billiard, a rectangular microwave billiard that contains a photonic crystal, are discussed. Close to the Dirac point states have been detected which are localized at the straight edge of the photonic crystal corresponding to a zigzag edge in graphene

Soccer: is scoring goals a predictable Poissonian process?

The non-scientific event of a soccer match is analysed on a strictly scientific level. The analysis is based on the recently introduced concept of a team fitness (Eur. Phys. J. B 67, 445, 2009) and requires the use of finite-size scaling. A uniquely defined function is derived which quantitatively predicts the expected average outcome of a soccer match in terms of the fitness of both teams. It is checked whether temporary fitness fluctuations of a team hamper the predictability of a soccer match. To a very good approximation scoring goals during a match can be characterized as independent Poissonian processes with pre-determined expectation values. Minor correlations give rise to an increase of the number of draws. The non-Poissonian overall goal distribution is just a consequence of the fitness distribution among different teams. The limits of predictability of soccer matches are quantified. Our model-free classification of the underlying ingredients determining the outcome of soccer matches can be generalized to different types of sports events

The Missing Link: Democratic Citizenship in Service Learning A Case Study of Undergraduate Course Offerings at a Large Urban University

The purpose of this study was to explore a discrete set of service-learning courses to determine. (1) were they of the type conducive to fostering democratic citizens. and (2) did the coordinating center that supported service-learning advocate it for democratic Citizenship. Sixteen university instructors and two administrative staff members from a coordinating center were interviewed, and documents describing the courses and coordinating center were reviewed. Drawing from the literature. a list of ten criteria for democratic citizenship was assembled, and two sets of questions-one for the instructors and another for the administrative staff-were devised to prompt the response of the participants. It was determined that: (1) the coordinating center exhibited nearly twice as many characteristics of democratic citizenship as did the instructors\u27 courses; (2) the coordinating center and the instructors had considerable room for improvement if democratic citizenship was a motivation and a goal for the students; (3) curricular interests were the primary reason for engaging in service learning; and (4) more support needs to be provided by the coordinating center if instructors are to gain confidence, and effectively develop service 1eaming for democratic citizenship

Application of a trace formula to the spectra of flat three-dimensional dielectric resonators

The length spectra of flat three-dimensional dielectric resonators of circular shape were determined from a microwave experiment. They were compared to a semiclassical trace formula obtained within a two-dimensional model based on the effective index of refraction approximation and a good agreement was found. It was necessary to take into account the dispersion of the effective index of refraction for the two-dimensional approximation. Furthermore, small deviations between the experimental length spectrum and the trace formula prediction were attributed to the systematic error of the effective index of refraction approximation. In summary, the methods developed in this article enable the application of the trace formula for two-dimensional dielectric resonators also to realistic, flat three-dimensional dielectric microcavities and -lasers, allowing for the interpretation of their spectra in terms of classical periodic orbits.Comment: 13 pages, 12 figures, 1 tabl

Experimental Observation of Localized Modes in a Dielectric Square Resonator

We investigated the frequency spectra and field distributions of a dielectric square resonator in a microwave experiment. Since such systems cannot be treated analytically, the experimental studies of their properties are indispensable. The momentum representation of the measured field distributions shows that all resonant modes are localized on specific classical tori of the square billiard. Based on these observations a semiclassical model was developed. It shows excellent agreement with all but a single class of measured field distributions that will be treated separately.Comment: 6 pages, 5 figures, 1 tabl