A TDDFT study of the excited states of DNA bases and their assemblies

We present a detailed study of the optical absorption spectra of DNA bases and base pairs, carried out by means of time dependent density functional theory. The spectra for the isolated bases are compared to available theoretical and experimental data and used to assess the accuracy of the method and the quality of the exchange-correlation functional: Our approach turns out to be a reliable tool to describe the response of the nucleobases. Furthermore, we analyze in detail the impact of hydrogen bonding and $\pi$-stacking in the calculated spectra for both Watson-Crick base pairs and Watson-Crick stacked assemblies. We show that the reduction of the UV absorption intensity (hypochromicity) for light polarized along the base-pair plane depends strongly on the type of interaction. For light polarized perpendicular to the basal plane, the hypochromicity effect is reduced, but another characteristic is found, namely a blue shift of the optical spectrum of the base-assembly compared to that of the isolated bases. The use of optical tools as fingerprints for the characterization of the structure (and type of interaction) is extensively discussed.Comment: 31 pages, 8 figure

Photo-excitation of a light-harvesting supra-molecular triad: a Time-Dependent DFT study

We present the first time-dependent density-functional theory (TDDFT) calculation on a light harvesting triad carotenoid-diaryl-porphyrin-C60. Besides the numerical challenge that the ab initio study of the electronic structure of such a large system presents, we show that TDDFT is able to provide an accurate description of the excited state properties of the system. In particular we calculate the photo-absorption spectrum of the supra-molecular assembly, and we provide an interpretation of the photo-excitation mechanism in terms of the properties of the component moieties. The spectrum is in good agreement with experimental data, and provides useful insight on the photo-induced charge transfer mechanism which characterizes the system.Comment: Accepted for publication on JPC, March 09th 200

Analytic theory of correlation energy and spin polarization in the 2D electron gas

We present an analytic theory of the pair distribution function and the ground-state energy in a two-dimensional (2D) electron gas with an arbitrary degree of spin polarization. Our approach involves the solution of a zero-energy scattering Schr\"odinger equation with an effective potential which includes a Fermi term from exchange and kinetic energy and a Bose-like term from Jastrow-Feenberg correlations. The form of the latter is assessed from an analysis of data on a 2D gas of charged bosons. We obtain excellent agreement with data from quantum Monte Carlo studies of the 2D electron gas. In particular, our results for the correlation energy show a quantum phase transition occurring at coupling strength $r_s\approx 24$ from the paramagnetic to the fully spin-polarized fluid.Comment: 9 pages, 4 figure

Spin magnetization of strongly correlated electron gas confined in a two-dimensional finite lattice

The influence of disorder and interaction on the ground state polarization of the two-dimensional (2D) correlated electron gas is studied by numerical investigations of unrestricted Hartree-Fock equations. The ferromagnetic ground state is found to be plausible when the electron number is lowered and the interaction and disorder parameters are suitably chosen. For a finite system at constant electronic density the disorder induced spin polarization is cut off when the electron orbitals become strongly localized to the individual network sites. The fluctuations of the interaction matrix elements are calculated and brought out as favoring the ferromagnetic instability in the extended and weak localization regime. The localization effect of the Hubbard interaction term is discussed.Comment: 7 pages, 9 figure

A tributação brasileira e o novo ambiente econômico: a reforma tributária inevitável e urgente

Bibliografia: p. 169-170Globalização, comércio eletrônico, concorrência acirrada: o ambiente econômico está mudando acelerada e profundamente. Exige harmonização internacional das instituições e das práticas tributárias, bem assim que se adotem tributos que provoquem o mínimo de distorções possíveis sobre o setor produtivo, as exportações e os investimentos, sob o risco (certo) de penalizar os países que forem menos eficazes na busca desses objetivos. Também no ambiente do federalismo a harmonização tributária começa pelo mercado interno, e crescem as idéias de que é necessário conciliar a concessão de ampla autonomia tributária e de gasto dos governos estaduais e municipais com uma disciplina austera que imponha a responsabilidade e o controle social. Todos esses fatores tornam a reforma do sistema tributário brasileiro um processo inadiável e premente. É a partir dessa ótica que este trabalho apresenta opiniões a respeito dos últimos passos da reforma tributária em discussão no Congresso Nacional desde 1995.Globalization, electronic commerce, and intense competition: the economic environment is changing profoundly and at a fast pace. This environment demands international cooperation between institutions and taxation practices. In addition, governments must adopt taxes that result in the least amount of distortion possible on production, exports and investments, with the clear risk of penalties for countries that are less effective in achieving these objectives. Another important factor is that within Brazil’s federation system improvements in taxation must first begin in the internal market. Within this structure it is necessary to conciliate the concession of ample autonomy in taxation and government spending at the state and local levels with austere discipline that imposes responsibility and social control. All of these factors create a situation in which the reform of Brazil’s tax system can no longer be postponed. In this light, this paper presents views on the most recent advances in the tax reform that has been under discussion in Congress since 1995

Self-consistent Overhauser model for the pair distribution function of an electron gas in dimensionalities D=3 and D=2

We present self-consistent calculations of the spin-averaged pair distribution function $g(r)$ for a homogeneous electron gas in the paramagnetic state in both three and two dimensions, based on an extension of a model that was originally proposed by A. W. Overhauser [Can. J. Phys. {\bf 73}, 683 (1995)] and further evaluated by P. Gori-Giorgi and J. P. Perdew [Phys. Rev. B {\bf 64}, 155102 (2001)]. The model involves the solution of a two-electron scattering problem via an effective Coulombic potential, that we determine within a self-consistent Hartree approximation. We find numerical results for $g(r)$ that are in excellent agreement with Quantum Monte Carlo data at low and intermediate coupling strength $r_s$, extending up to $r_s\approx 10$ in dimensionality D=3. However, the Hartree approximation does not properly account for the emergence of a first-neighbor peak at stronger coupling, such as at $r_s=5$ in D=2, and has limited accuracy in regard to the spin-resolved components $g_{\uparrow\uparrow}(r)$ and $g_{\uparrow\downarrow}(r)$. We also report calculations of the electron-electron s-wave scattering length, to test an analytical expression proposed by Overhauser in D=3 and to present new results in D=2 at moderate coupling strength. Finally, we indicate how this approach can be extended to evaluate the pair distribution functions in inhomogeneous electron systems and hence to obtain improved exchange-correlation energy functionals.Comment: 14 pages, 7 figuers, to apear in Physical Review

Excitonic condensation in a symmetric electron-hole bilayer

Using Diffusion Monte Carlo simulations we have investigated the ground state of a symmetric electron-hole bilayer and determined its phase diagram at T=0. We find clear evidence of an excitonic condensate, whose stability however is affected by in-layer electronic correlation. This stabilizes the electron-hole plasma at large values of the density or inter-layer distance, and the Wigner crystal at low density and large distance. We have also estimated pair correlation functions and low order density matrices, to give a microscopic characterization of correlations, as well as to try and estimate the condensate fraction.Comment: 4 pages, 3 figures, 2 table

Tight-binding parameters for charge transfer along DNA

We systematically examine all the tight-binding parameters pertinent to charge transfer along DNA. The $\pi$ molecular structure of the four DNA bases (adenine, thymine, cytosine, and guanine) is investigated by using the linear combination of atomic orbitals method with a recently introduced parametrization. The HOMO and LUMO wavefunctions and energies of DNA bases are discussed and then used for calculating the corresponding wavefunctions of the two B-DNA base-pairs (adenine-thymine and guanine-cytosine). The obtained HOMO and LUMO energies of the bases are in good agreement with available experimental values. Our results are then used for estimating the complete set of charge transfer parameters between neighboring bases and also between successive base-pairs, considering all possible combinations between them, for both electrons and holes. The calculated microscopic quantities can be used in mesoscopic theoretical models of electron or hole transfer along the DNA double helix, as they provide the necessary parameters for a tight-binding phenomenological description based on the $\pi$ molecular overlap. We find that usually the hopping parameters for holes are higher in magnitude compared to the ones for electrons, which probably indicates that hole transport along DNA is more favorable than electron transport. Our findings are also compared with existing calculations from first principles.Comment: 15 pages, 3 figures, 7 table

The Political Economy of Domestic Tax Reform in Bangladesh: Political Settlements, Informal Institutions and the Negotiation of Reform

This paper explains the persistence of a tax system characterised by low revenue collection and extensive informality in Bangladesh. It combines analysis of long-term formal and informal institutions and of micro-level incentives shaping negotiation of short-term reform. The system is unusually informal, discretionary, and corrupt, but remains resistant to change because it delivers low and predictable tax rates to business, extensive opportunities for corruption to the tax administration, and an important vehicle for fundraising by political leaders and rent distribution to their elite supporters. We then explore the dynamics of micro-level reform and external pressure within the constraints of this overarching political bargain

Surplus Photosynthetic Antennae Complexes Underlie Diagnostics of Iron Limitation in a Cyanobacterium

Chlorophyll fluorescence from phytoplankton provides a tool to assess iron limitation in the oceans, but the physiological mechanism underlying the fluorescence response is not understood. We examined fluorescence properties of the model cyanobacterium Synechocystis PCC6803 and a ΔisiA knock-out mutant of the same species grown under three culture conditions which simulate nutrient conditions found in the open ocean: (1) nitrate and iron replete, (2) limiting-iron and high-nitrate, representative of natural high-nitrate, low-chlorophyll regions, and (3) iron and nitrogen co-limiting. We show that low variable fluorescence, a key diagnostic of iron limitation, results from synthesis of antennae complexes far in excess of what can be accommodated by the iron-restricted pool of photosynthetic reaction centers. Under iron and nitrogen co-limiting conditions, there are no excess antennae complexes and variable fluorescence is high. These results help to explain the well-established fluorescence characteristics of phytoplankton in high-nutrient, low-chlorophyll ocean regions, while also accounting for the lack of these properties in low-iron, low-nitrogen regions. Importantly, our results complete the link between unique molecular consequences of iron stress in phytoplankton and global detection of iron stress in natural populations from space