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At least 91 records · Page 5Linked to original sources
PubMed2002

Suppression of electron-hole correlations in 3D polymer materials.

We present an ab initio study of the optical absorption spectra of isolated as well as crystalline trans-polyacetylene. We include excitonic effects by solving the Bethe-Salpeter equation for the electron-hole two-particle correlation function. We observe that the strength of the electron-hole interactions drastically reduces when going from an isolated polymer chain to a crystalline arrangement. This is not only a result of enhanced screening in the 3D material, but also of the increased spatial extent of the exciton perpendicular to the polymer chains. We point out that these findings apply to crystalline phases of conjugated polymers and molecular crystals in general.

Journal Article↗
PubMed2005

A physical model for the longitudinal polarizabilities of polymer chains.

The aim of this work is to provide a physical model to relate the polarizability per unit cell of oligomers to that of their corresponding infinite polymer chains. For this we propose an extrapolation method for the polarizability per unit cell of oligomers by fitting them to a physical model describing the dielectric properties of polymer chains. This physical model is based on the concept of a dielectric needle in which we assume a polymer chain to be well described by a cylindrically shaped nonconducting rod with a radius much smaller than its length. With this model we study in which way the polarizability per unit cell approaches the limit of the infinite chain. We show that within this model the macroscopic contribution of the induced electric field to the macroscopic electric field vanishes in the limit of an infinite polymer chain, i.e., there is no macroscopic screening. The macroscopic electric field becomes equal to the external electric field in this limit. We show that this identification leads to a relation between the polarizability per unit cell and the electric susceptibility of the infinite polymer chain. We test our dielectric needle model on the polarizability per unit cell of oligomers of the hydrogen chain and polyacetylene obtained earlier using time-dependent current-density-functional theory in the adiabatic local-density approximation and with the Vignale-Kohn functional. We also perform calculations using the same theory on truly infinite polymer chains by employing periodic boundary conditions. We show that by extrapolating the oligomer results according to our dielectric needle model we get good agreement with our results from calculations on the corresponding infinite polymer chains.

Journal Article↗
PubMed2005

Enantioselective esterification of prochiral phosphonate pendants of a polyphenylacetylene assisted by macromolecular helicity: storage of a dynamic macromolecular helicity memory.

A poly(phenylacetylene) bearing a phosphonic acid monoethyl ester as the pendant forms a one-handed helical structure induced by an optically active amine, and this helicity can be "memorized"after the amine is replaced by achiral diamines. The helicity memory lasts for an extremely long time but spontaneously disappears after the achiral diamines are removed by a stronger acid, indicating the dynamic nature of the helicity memory. Here we report that such a dynamic memory could be "stored" after the pendant was converted to its methyl ester with diazomethane, resulting in the generation of a phosphorus stereogenic center with optical activity. The esterification enantioselectively proceeded through chirality transfer from the induced helical conformation or the helicity memory of the polyacetylene backbone. Although the enantioselectivity was low, the pendant chirality was significantly amplified in the polymer backbone at low temperatures, resulting in higher optical activity as an excess single-handed helix than that expected from the enantiomeric excess of the pendants.

Journal Article↗
PubMed2005

Spatial tissue distribution of polyacetylenes in carrot root.

The presented results show the usefulness of Raman spectroscopy in the investigation of polyacetylenes in carrot root. The components are measured directly in the plant tissue without any preliminary sample preparation. Compared with the strong polyacetylene signals the spectral impact of the surrounding biological matrix is weak, except for carotenoids, and therefore it does not contribute significantly to the obtained results. Three different Raman mapping techniques applied here have revealed essential information about the investigated compounds. Using point acquisition several spectra have been measured to demonstrate the complex composition of the polyacetylene fraction in carrot root. The molecular structures of falcarinol, falcarindiol and falcarindiol 3-acetate are similar but their Raman spectra exhibit differences demonstrated by the shift of their -C triple bond C- mode. Line mapping performed along the diameter of transversely cut carrot roots has been used to investigate the relative concentration of polyacetylenes and carotenoids. An area map provides detailed information regarding the distribution of both components. It has been found that high accumulation of polyacetylenes is located in the outer section of the root, namely the pericyclic parenchyma, and in the phloem part close to the secondary cambium. The highest concentration of carotenes is seen in the immediate vicinity to polyacetylene conglomerates.

Acetylene↗
PubMed2004

Raman spectroscopy of amorphous, nanostructured, diamond-like carbon, and nanodiamond.

Raman spectroscopy is a standard characterization technique for any carbon system. Here we review the Raman spectra of amorphous, nanostructured, diamond-like carbon and nanodiamond. We show how to use resonant Raman spectroscopy to determine structure and composition of carbon films with and without nitrogen. The measured spectra change with varying excitation energy. By visible and ultraviolet excitation measurements, the G peak dispersion can be derived and correlated with key parameters, such as density, sp(3) content, elastic constants and chemical composition. We then discuss the assignment of the peaks at 1150 and 1480 cm(-1) often observed in nanodiamond. We review the resonant Raman, isotope substitution and annealing experiments, which lead to the assignment of these peaks to trans-polyacetylene.

Acetylene↗
PubMed2006

Functional disubstituted polyacetylenes: Synthesis, liquid crystallinity, light emission, and fluorescent photopatterning of biphenyl-containing poly(1-phenyl-octyne)s with different functional bridges.

Biphenyl (Biph)-containing 1-phenyl-1-octynes and their polymers are synthesized, and the effects of functional bridge groups on the mesomorphic and optical properties of the polymers are studied. The nonmesomorphic disubstituted acetylene monomers (C6H13)C[triple bond]C(C6H4)O(CH2)12O-Biph-OC7H15 (1), (C6H13)C[triple bond]C(C6H4)O(CH2)11OOC-Biph-OC7H15 (2), and (C6H13)C[triple bond]C(C6H4)CO2(CH2)12OOC-Biph-OC7H15 (3) are prepared by multistep reaction routes and converted into their corresponding polymers P1-P3 by a WCl6-Ph4Sn catalyst. The structures and properties of the polymers are characterized and evaluated by NMR, TGA, DSC, POM, XRD, UV, and PL analyses. The mesogenic pendants have endowed the polymers with high thermal stability (> or =400 degrees C). While P1 exhibits no liquid crystallinity, P2 and P3 form enantiotropic S(A) phase with a monolayer structure. Upon photoexcitation, the polymers emit blue and blue-green lights of 460 and 480 nm, respectively, in THF with quantum efficiencies larger than 30%. UV irradiation of a thin film of P2 through a mask oxidizes and quenches the light emission of the exposed regions, generating a two-dimensional luminescent photoimage.

Journal Article↗
PubMed2004

Coupled-cluster singles and doubles for extended systems.

Coupled-cluster theory with connected single and double excitation operators (CCSD) and related approximations, such as linearized CCSD, quadratic configuration interaction with single and double excitation operators, coupled-cluster with connected double excitation operator (CCD), linearized CCD, approximate CCD, and second- and third-order many-body perturbation theories, are formulated and implemented for infinitely extended one-dimensional systems (polymers), on the basis of the periodic boundary conditions and distance-based screening of integrals, density matrix elements, and excitation amplitudes. The variation of correlation energies with the truncation radii of short- and long-range lattice sums and with the number of wave vector sampling points in the first Brillouin zone is examined for polyethylene, polyacetylene, and polyyne, and is shown to be a function of the degree of pi-electron conjugation or the fundamental band gaps. The t2 and t1 amplitudes in the atomic orbital (AO) basis are obtained by first computing the t amplitudes in the Bloch-orbital basis and subsequently back-transforming them into the AO basis. The plot of these AO-based t amplitudes as a function of unit cells also indicates that the t2 amplitudes of polyacetylene and polyyne exhibit appreciably slower decay than those of polyethylene, although the asymptotic decay behavior is invariably 1/r3. The AO-based t1 amplitudes appear to correlate strongly with the electronic structure, and they decay seemingly exponentially for polyethylene whereas they stay at a constant magnitude across the seventh nearest neighbors of polyacetylene and polyyne, which attests to far reaching effects of nondynamical electron correlation mediated by orbital rotation. Nonetheless, the unit cell contributions to the correlation energies taper below 10(-6) hartree after 15 A for all three polymers. The basis set dependence of the decay behavior of t2 amplitudes is also examined for linear hydrogen fluoride polymer (HF)infinity and linear beryllium polymer (Be)infinity employing the STO-3G, 6-31G, and 6-31G* basis sets, and proves to be rather small.

Journal Article↗
PubMed2005

Controlling bending and twisting of conjugated polymers via solitons.

A strong generic coupling between self-localized solitons and conformations of a pi-conjugated polymer chain is demonstrated through ab initio calculations and the underlying mechanisms revealed by using an extended Hubbard model. We show that significant chain bending and twisting of trans- and cis-polyacetylene result from torque imbalances among atom-centered orbitals and the steric instability at single-bond cis-centers, respectively. The soliton-induced conformational effects create sufficient strains to provide an intrinsic high-strain-rate actuation mechanism in optical excitation processes.

Algorithms↗
PubMed2004

Nonracemic dopant-mediated hierarchical amplification of macromolecular helicity in a charged polyacetylene leading to a cholesteric liquid crystal in water.

Here we show the first example of a helical polyacetylene that forms a lyotropic liquid crystal (LC) through a hierarchical amplification of a macromolecular helicity process in water. The macromolecular helicity with an excess of one helical sense was first induced in the positively charged polyacetylene upon complexation with an extremely small oppositely charged nonracemic dopant through electrostatic interaction in water. Subsequently, the helicity was significantly amplified in the polymer backbone as an almost perfect single-handed helix through self-assembly into supramolecular helical arrays in a lyotropic cholesteric state. The present results will allow the detection of a tiny imbalance in chiral molecules and also provide new approaches for the design of novel water-soluble helical architectures and the construction of new chiral materials in areas such as biotechnology and materials science.

Acetylene↗
PubMed2004

Helical polymer carrying helical grafts from peptide-based acetylene macromonomers: synthesis.

N-Propargylamide-terminated peptide-based macromonomers with a degree of polymerization ranging from 4 to 40 were synthesized by the polymerization of gamma-benzyl and gamma-stearyl-L-glutamate-N-carboxy anhydrides initiated with propargylamine. The macromonomers took an alpha-helical structure, which was confirmed by signals at 208 and 220 nm in CD spectra. The macromonomers were subjected to polymerization and copolymerization with an alanine-derived N-propargylamide [N-(tert-butoxycarbonyl)-L-alanine-N'-propargylamide] catalyzed with (2,5-norbornadiene)Rh+[eta6-C6H5B- (C6H5)3]. It was confirmed through a CD spectroscopic study that the copolymer obtained from the copolymerization of the gamma-stearyl-L-glutamate-based macromonomer with the alanine-derived N-propargylamide had a helical polyacetylene main chain and helical polypeptide side chains.

Acetylene↗