We employ two tight-binding (TB) approaches to systematically study the electronic structure and hole or electron transfer in B-DNA monomer polymers and dimer polymers made up of monomers (base pairs): (I) at the base-pair level, using the onsite energies of base pairs and the hopping integrals between successive base pairs, i.e., a wire model and (II) at the single-base level, using the onsite energies of the bases and the hopping integrals between neighboring bases, i.e., an extended ladder model since we also include diagonal hoppings. We solve a system of (matrix dimension) coupled equations [(I) , (II) for the time-independent problem, and a system of coupled first order differential equations for the time-dependent problem. We perform a comparative study of stationary and time-dependent aspects of the two TB variants, using realistic sets of parameters. The studied properties include HOMO and LUMO eigenspectra, occupation probabilities, density of states and HOMO-LUMO gaps as well as mean over time probabilities to find the carrier at each site [(I) base pair or (II) base], Fourier spectra, which reflect the frequency content of charge transfer, and pure mean transfer rates from a certain site to another. The two TB approaches give coherent, complementary aspects of electronic properties and charge transfer in B-DNA monomer polymers and dimer polymers.
Hydrochemical and isotopic characteristics of fluids from major geothermal fields of middle/low temperature in N/NE Greece are examined [basins: Strymon River (SR), Nestos River Delta (ND), Xanthi–Komotini (XK), Loutros–Feres–Soufli (LFS) and Rhodope Massif]. The geodynamic context is reflected to isotopic/chemical composition of fluids, heat flow values and elevated CO2 concentrations in emitted fluids. B and Li are derived from leaching of the geothermal systems hosting rocks. δ18OH2O, δ18OSO4, δ13CCO2 values and chemical compositions of Cl, B and Li of geothermal discharges suggest two distinct source fluids. Fluids in SR exhibit high B/Cl and Li/Cl ratios, suggesting these constituents are derived from associated magmas of intermediate composition (andesitic rocks). Geothermal discharges in LFS exhibit low B/Cl and Li/Cl ratios, implying acid (rhyolitic) magmatism. δ13CCO2 and CO2/(CO2 + 105He) ratios in the west part, suggest fluids affected by addition of volatiles released from subducted marine sediments. For the eastern systems, these ratios suggest gas encountered in systems issued from mixing of crustal and mantle-derived volatiles. Isotopic geothermometers reflect, for the same direction, equilibrium processes more (LFS, XK) or less (SR) pronounced and discriminate the geothermal field from low to middle [SR, ND (Erasmio)] and middle to high enthalpy [ND (Eratino), LFS, XK].
5 March 2012 in International Journal of Quantum Chemistry