Browsing by Subject "Models, Chemical"

Now showing 1 - 4 of 4

Open Access
Effects of perfluorination on thiophene and pyrrole oligomers
(2010) Salzner, U.
The effect of perfluorination on thiophene and pyrrole oligomers in neutral, cationic, and anionic states was investigated with density functional theory at the (TD)B3P86-30%/6-31G* level. For the title compounds fluorination leads to planarization. For pyrroles a band gap reduction of 0.58 eV results, as unsubstituted pyrroles are nonplanar and disordered in the solid state. For thiophene the band gap is slightly increased as long thiophene oligomers are almost planar. Ionization energies and electron affinities increase upon fluorination by 0.65 and 0.60 eV for polythiophene and by 0.45 and 0.90 eV for polypyrrole. Conduction band widths increase by 0.5 for polythiophene and by 0.7 eV for polypyrrole. Spectra of charged (doped) forms are almost identical to those of the parent systems. Like parent systems, fluorinated oligomers with chain lengths of more than six rings develop a third UV absorption that increases in strength and decreases in energy upon chain length increase.
Open Access
Electrostatics of Polymer Translocation Events in Electrolyte Solutions
(American Institute of Physics Inc., 2016) Buyukdagli, S.; Ala-Nissila, T.
We develop an analytical theory that accounts for the image and surface charge interactions between a charged dielectric membrane and a DNA molecule translocating through the membrane. Translocation events through neutral carbon-based membranes are driven by a competition between the repulsive DNA-image-charge interactions and the attractive coupling between the DNA segments on the trans and the cis sides of the membrane. The latter effect is induced by the reduction of the coupling by the dielectric membrane. In strong salt solutions where the repulsive image-charge effects dominate the attractive trans-cis coupling, the DNA molecule encounters a translocation barrier of ∼10 kBT. In dilute electrolytes, the trans-cis coupling takes over image-charge forces and the membrane becomes a metastable attraction point that can trap translocating polymers over long time intervals. This mechanism can be used in translocation experiments in order to control DNA motion by tuning the salt concentration of the solution.
Open Access
Ionic current inversion in pressure-driven polymer translocation through nanopores
(American Physical Society, 2015) Buyukdagli, S.; Blossey, R.; Ala-Nissila, T.
We predict streaming current inversion with multivalent counterions in hydrodynamically driven polymer translocation events from a correlation-corrected charge transport theory including charge fluctuations around mean-field electrostatics. In the presence of multivalent counterions, electrostatic many-body effects result in the reversal of the DNA charge. The attraction of anions to the charge-inverted DNA molecule reverses the sign of the ionic current through the pore. Our theory allows for a comprehensive understanding of the complex features of the resulting streaming currents. The underlying mechanism is an efficient way to detect DNA charge reversal in pressure-driven translocation experiments with multivalent cations. © 2015 American Physical Society.
Open Access
Light-induced pitch transitions in photosensitive cholesteric liquid crystals: Effects of anchoring energy
(American Physical Society, 2014) Orlova, T. N.; Iegorov, R. I.; Kiselev, A. D.
We experimentally study how the cholesteric pitch P depends on the equilibrium pitch P0 in planar liquid crystal (LC) cells with both strong and semistrong anchoring conditions. The cholesteric phase was induced by dissolution in the nematic LC of the right-handed chiral dopant 7-dehydrocholesterol (7-DHC, provitamin D3) which transforms to left-handed tachysterol under the action of uv irradiation at the wavelength of 254 nm. By using the model of photoreaction kinetics we obtain the dependencies of isomer concentrations and, therefore, of the equilibrium pitch on the uv irradiation dose. The cholesteric pitch was measured as a function of irradiation time using the polarimetry method. In this method, the pitch is estimated from the experimental data on the irradiation time dependence of the ellipticity of light transmitted through the LC cells. It is found that the resulting dependence of the twist parameter 2D/P (D is the cell thickness) on the free twisting number parameter 2D/P0 shows jumplike behavior and agrees well with the known theoretical results for the anchoring potential of Rapini-Papoular form. © 2014 American Physical Society.