A simplified picture for Pi electrons in conjugated polymers : from PPP Hamiltonian to an effective molecular crystal approach

An excitonic method proper to study conjugated oligomers and polymers is described and its applicability tested on the ground state and first excited states of trans-polyacetylene, taken as a model. From the Pariser-Parr-Pople Hamiltonian, we derive an effective Hamiltonian based on a local description of the polymer in term of monomers; the relevant electronic configurations are build on a small number of pertinent local excitations. The intuitive and simple microscopic physical picture given by our model supplement recent results, such as the Rice and Garstein ones. Depending of the parameters, the linear absorption appears dominated by an intense excitonic peak.Comment: 41 Pages, 6 postscript figure

National Mesothelioma Virtual Bank: A standard based biospecimen and clinical data resource to enhance translational research

Background: Advances in translational research have led to the need for well characterized biospecimens for research. The National Mesothelioma Virtual Bank is an initiative which collects annotated datasets relevant to human mesothelioma to develop an enterprising biospecimen resource to fulfill researchers' need. Methods: The National Mesothelioma Virtual Bank architecture is based on three major components: (a) common data elements (based on College of American Pathologists protocol and National North American Association of Central Cancer Registries standards), (b) clinical and epidemiologic data annotation, and (c) data query tools. These tools work interoperably to standardize the entire process of annotation. The National Mesothelioma Virtual Bank tool is based upon the caTISSUE Clinical Annotation Engine, developed by the University of Pittsburgh in cooperation with the Cancer Biomedical Informatics Grid™ (caBIG™, see http://cabig.nci.nih.gov). This application provides a web-based system for annotating, importing and searching mesothelioma cases. The underlying information model is constructed utilizing Unified Modeling Language class diagrams, hierarchical relationships and Enterprise Architect software. Result: The database provides researchers real-time access to richly annotated specimens and integral information related to mesothelioma. The data disclosed is tightly regulated depending upon users' authorization and depending on the participating institute that is amenable to the local Institutional Review Board and regulation committee reviews. Conclusion: The National Mesothelioma Virtual Bank currently has over 600 annotated cases available for researchers that include paraffin embedded tissues, tissue microarrays, serum and genomic DNA. The National Mesothelioma Virtual Bank is a virtual biospecimen registry with robust translational biomedical informatics support to facilitate basic science, clinical, and translational research. Furthermore, it protects patient privacy by disclosing only de-identified datasets to assure that biospecimens can be made accessible to researchers. © 2008 Amin et al; licensee BioMed Central Ltd

Centre-of-mass separation in quantum mechanics: Implications for the many-body treatment in quantum chemistry and solid state physics

We address the question to what extent the centre-of-mass (COM) separation can change our view of the many-body problem in quantum chemistry and solid state physics. It was shown that the many-body treatment based on the electron-vibrational Hamiltonian is fundamentally inconsistent with the Born-Handy ansatz so that such a treatment can never respect the COM problem. Born-Oppenheimer (B-O) approximation reveals some secret: it is a limit case where the degrees of freedom can be treated in a classical way. Beyond the B-O approximation they are inseparable in principle. The unique covariant description of all equations with respect to individual degrees of freedom leads to new types of interaction: besides the known vibronic (electron-phonon) one the rotonic (electron-roton) and translonic (electron-translon) interactions arise. We have proved that due to the COM problem only the hypervibrations (hyperphonons, i.e. phonons + rotons + translons) have true physical meaning in molecules and crystals; nevertheless, the use of pure vibrations (phonons) is justified only in the adiabatic systems. This fact calls for the total revision of our contemporary knowledge of all non-adiabatic effects, especially the Jahn-Teller effect and superconductivity. The vibronic coupling is responsible only for removing of electron (quasi)degeneracies but for the explanation of symmetry breaking and forming of structure the rotonic and translonic coupling is necessary.Comment: 39 pages, 11 sections, 3 appendice

Molecular crystal approach for pi-conjugated polymers: from PPP Hamiltonian to Holstein model for polaron states

Starting from the $\pi$-electron Pariser-Parr-Pople (PPP) Hamiltonian which includes both strong electron-phonon and electron-electron interactions, we propose some strongly correlated wave functions of increasing quality for the ground state of conjugated polymers. These wavefunctions are built by combining different finite sets of local configurations extended at most over two nearest-neighbour monomers. With this picture, the doped case with one additional particle is expressed in terms of quasi-particle. Thus, the polaron formation problem goes back to the study of a Holstein like model.Comment: 27 pages, 6 eps figs, Revtex; enlarged version. Submitted to Journal of Physics: Condensed Matte

Structural Instability in Polyacene : A Projector Quantum Monte Carlo Study

We have studied polyacene within the Hubbard model to explore the effect of electron correlations on the Peierls' instability in a system marginally away from one-dimension. We employ the projector quantum Monte Carlo method to obtain ground state estimates of the energy and various correlation functions. We find strong similarities between polyacene and polyacetylene which can be rationalized from the real-space valence-bond arguments of Mazumdar and Dixit. Electron correlations tend to enhance the Peierls' instability in polyacene. This enhancement appears to attain a maximum at $U/t \sim 3.0$ and the maximum shifts to larger values when the alternation parameter is increased. The system shows no tendency to destroy the imposed bond-alternation pattern, as evidenced by the bond-bond correlations. The cis- distortion is seen to be favoured over the trans- distortion. The spin-spin correlations show that undistorted polyacene is susceptible to a SDW distortion for large interaction strength. The charge-charge correlations indicate the absence of a CDW distortion for the parameters studied.Comment: 13 pages, 10 figures available on reques

Prediction of infrared light emission from pi-conjugated polymers: a diagrammatic exciton basis valence bond theory

There is currently a great need for solid state lasers that emit in the infrared, as this is the operating wavelength regime for applications in telecommunications. Existing $\pi$--conjugated polymers all emit in the visible or ultraviolet, and whether or not $\pi$--conjugated polymers that emit in the infrared can be designed is an interesting challenge. On the one hand, the excited state ordering in trans-polyacetylene, the $\pi$--conjugated polymer with relatively small optical gap, is not conducive to light emission because of electron-electron interaction effects. On the other hand, excited state ordering opposite to that in trans-polyacetylene is usually obtained by chemical modification that increases the effective bond-alternation, which in turn increases the optical gap. We develop a theory of electron correlation effects in a model $\pi$-conjugated polymer that is obtained by replacing the hydrogen atoms of trans-polyacetylene with transverse conjugated groups, and show that the effective on-site correlation in this system is smaller than the bare correlation in the unsubstituted system. An optical gap in the infrared as well as excited state ordering conducive to light emission is thereby predicted upon similar structural modifications.Comment: 15 pages, 15 figures, 1 tabl

Many-body-QED perturbation theory: Connection to the Bethe-Salpeter equation

The connection between many-body theory (MBPT)--in perturbative and non-perturbative form--and quantum-electrodynamics (QED) is reviewed for systems of two fermions in an external field. The treatment is mainly based upon the recently developed covariant-evolution-operator method for QED calculations [Lindgren et al. Phys. Rep. 389, 161 (2004)], which has a structure quite akin to that of many-body perturbation theory. At the same time this procedure is closely connected to the S-matrix and the Green's-function formalisms and can therefore serve as a bridge between various approaches. It is demonstrated that the MBPT-QED scheme, when carried to all orders, leads to a Schroedinger-like equation, equivalent to the Bethe-Salpeter (BS) equation. A Bloch equation in commutator form that can be used for an "extended" or quasi-degenerate model space is derived. It has the same relation to the BS equation as has the standard Bloch equation to the ordinary Schroedinger equation and can be used to generate a perturbation expansion compatible with the BS equation also for a quasi-degenerate model space.Comment: Submitted to Canadian J of Physic

Thermodynamic perturbation theory for dipolar superparamagnets

Thermodynamic perturbation theory is employed to derive analytical expressions for the equilibrium linear susceptibility and specific heat of lattices of anisotropic classical spins weakly coupled by the dipole-dipole interaction. The calculation is carried out to the second order in the coupling constant over the temperature, while the single-spin anisotropy is treated exactly. The temperature range of applicability of the results is, for weak anisotropy (A/kT << 1), similar to that of ordinary high-temperature expansions, but for moderately and strongly anisotropic spins (A/kT > 1) it can extend down to the temperatures where the superparamagnetic blocking takes place (A/kT \sim 25), provided only the interaction strength is weak enough. Besides, taking exactly the anisotropy into account, the results describe as particular cases the effects of the interactions on isotropic (A = 0) as well as strongly anisotropic (A \to \infty) systems (discrete orientation model and plane rotators).Comment: 15 pages, 3 figure

Electron correlation effects in electron-hole recombination in organic light-emitting diodes

We develop a general theory of electron--hole recombination in organic light emitting diodes that leads to formation of emissive singlet excitons and nonemissive triplet excitons. We briefly review other existing theories and show how our approach is substantively different from these theories. Using an exact time-dependent approach to the interchain/intermolecular charge-transfer within a long-range interacting model we find that, (i) the relative yield of the singlet exciton in polymers is considerably larger than the 25% predicted from statistical considerations, (ii) the singlet exciton yield increases with chain length in oligomers, and, (iii) in small molecules containing nitrogen heteroatoms, the relative yield of the singlet exciton is considerably smaller and may be even close to 25%. The above results are independent of whether or not the bond-charge repulsion, X_perp, is included in the interchain part of the Hamiltonian for the two-chain system. The larger (smaller) yield of the singlet (triplet) exciton in carbon-based long-chain polymers is a consequence of both its ionic (covalent) nature and smaller (larger) binding energy. In nitrogen containing monomers, wavefunctions are closer to the noninteracting limit, and this decreases (increases) the relative yield of the singlet (triplet) exciton. Our results are in qualitative agreement with electroluminescence experiments involving both molecular and polymeric light emitters. The time-dependent approach developed here for describing intermolecular charge-transfer processes is completely general and may be applied to many other such processes.Comment: 19 pages, 11 figure