Stacking of oligo and polythiophenes cations in solution: surface tension and dielectric saturation

The stacking of positively charged (or doped) terthiophene oligomers and quaterthiophene polymers in solution is investigated applying a recently developed unified electrostatic and cavitation model for first-principles calculations in a continuum solvent. The thermodynamic and structural patterns of the dimerization are explored in different solvents, and the distinctive roles of polarity and surface tension are characterized and analyzed. Interestingly, we discover a saturation in the stabilization effect of the dielectric screening that takes place at rather small values of $\epsilon_0$. Moreover, we address the interactions in trimers of terthiophene cations, with the aim of generalizing the results obtained for the dimers to the case of higher-order stacks and nanoaggregates

Population and Size Distribution of Small Jovian Trojan Asteroids

We present a study of Jovian Trojan objects detected serendipitously during the course of a sky survey conducted at the University of Hawaii 2.2-meter telescope. We used a 8192 x 8192 pixel charge-coupled device (CCD) mosaic to observe 20 deg^2 at locations spread over the L4 Lagrangian swarm and reached a limiting magnitude V = 22.5 mag (50% of maximum detection efficiency). Ninety-three Jovian Trojans were detected with radii 2 - 20 km (assumed albedo 0.04). Their differential magnitude distribution has a slope of 0.40 +/- 0.05 corresponding to a power law size distribution index 3.0 +/- 0.3 (1-sigma). The total number of L4 Trojans with radii > 1 km is of order 1.6 x 10^5 and their combined mass (dominated by the largest objects) is ~ 10^{-4} M_{Earth}. The bias-corrected mean inclination is 13.7 +/- 0.5 deg. We also discuss the size and spatial distribution of the L4 swarm.Comment: 21 pages, 11 figures. AJ, in pres

Dielectric Response of Periodic Systems from Quantum Monte Carlo Calculations

We present a novel approach that allows to calculate the dielectric response of periodic systems in the quantum Monte Carlo formalism. We employ a many-body generalization for the electric enthalpy functional, where the coupling with the field is expressed via the Berry-phase formulation for the macroscopic polarization. A self-consistent local Hamiltonian then determines the ground-state wavefunction, allowing for accurate diffusion quantum Monte Carlo calculations where the polarization's fixed point is estimated from the average on an iterative sequence, sampled via forward-walking. This approach has been validated for the case of an isolated hydrogen atom, and then applied to a periodic system, to calculate the dielectric susceptibility of molecular-hydrogen chains. The results found are in excellent agreement with the best estimates obtained from the extrapolation of quantum-chemistry calculations.Comment: 5 page 2figure

Simulation of Heme using DFT+U: a step toward accurate spin-state energetics

We investigate the DFT+U approach as a viable solution to describe the low-lying states of ligated and unligated iron heme complexes. Besides their central role in organometallic chemistry, these compounds represent a paradigmatic case where LDA, GGA, and common hybrid functionals fail to reproduce the experimental magnetic splittings. In particular, the imidazole pentacoordinated heme is incorrectly described as a triplet by all usual DFT flavors. In this study we show that a U parameter close to 4 eV leads to spin transitions and molecular geometries in quantitative agreement with experiments, and that DFT+U represents an appealing tool in the description of iron porphyrin complexes, at a much reduced cost compared to correlated quantum-chemistry methods. The possibility of obtaining the U parameter from first-principles is explored through a self-consistent linear-response formulation. We find that this approach, which proved to be successful in other iron systems, produces in this case some overestimation with respect to the optimal values of U.Comment: To be published in The Journal of Physical Chemistry B 30 pages, 15 figure

Taxonomy of asteroid families among the Jupiter Trojans: Comparison between spectroscopic data and the Sloan Digital Sky Survey colors

We present a comparative analysis of the spectral slope and color distributions of Jupiter Trojans, with particular attention to asteroid families. We use a sample of data from the Moving Object Catalogue of the Sloan Digital Sky Survey, together with spectra obtained from several surveys. A first sample of 349 observations, corresponding to 250 Trojan asteroids, were extracted from the Sloan Digital Sky Survey, and we also extracted from the literature a second sample of 91 spectra, corresponding to 71 Trojans. The spectral slopes were computed by means of a least-squares fit to a straight line of the fluxes obtained from the Sloan observations in the first sample, and of the rebinned spectra in the second sample. In both cases the reflectance fluxes/spectra were renormalized to 1 at 6230 $\textrm{\AA}$. We found that the distribution of spectral slopes among Trojan asteroids shows a bimodality. About 2/3 of the objects have reddish slopes compatible with D-type asteroids, while the remaining bodies show less reddish colors compatible with the P-type and C-type classifications. The members of asteroid families also show a bimodal distribution with a very slight predominance of D-type asteroids, but the background is clearly dominated by the D-types. The L4 and L5 swarms show different distributions of spectral slopes, and bimodality is only observed in L4. These differences can be attributed to the asteroid families since the backgraound asteroids show the same slope distribtuions in both swarms. The analysis of individual families indicates that the families in L5 are taxonomically homogeneous, but in L4 they show a mixture of taxonomic types. We discuss a few scenarios that might help to interpret these results.Comment: 20 pages, 15 figures, 2 table

Transition state method and Wannier functions

We propose a computational scheme for materials where standard Local Density Approximation (LDA) fails to produce a satisfactory description of excitation energies. The method uses Slater's "transition state" approximation and Wannier functions basis set. We define a correction to LDA functional in such a way that its variation produces one-electron energies for Wannier functions equal to the energies obtained in "transition state" constrained LDA calculations. In the result eigenvalues of the proposed functional could be interpreted as excitation energies of the system under consideration. The method was applied to MgO, Si, NiO and BaBiO$_3$ and gave an improved agreement with experimental data of energy gap values comparing with LDA.Comment: 13 pages, 6 figures, 1 tabl

Effect of rotational disruption on the size-frequency distribution of the Main Belt asteroid population

The size distribution of small asteroids in the Main Belt is assumed to be determined by an equilibrium between the creation of new bodies out of the impact debris of larger asteroids and the destruction of small asteroids by collisions with smaller projectiles. However, for a diameter less than 6 km we find that YORP-induced rotational disruption significantly contributes to the erosion even exceeding the effects of collisional fragmentation. Including this additional grinding mechanism in a collision evolution model for the asteroid belt, we generate size-frequency distributions from either an accretional (Weidenschilling, 2011) or an "Asteroids were born big" (Morbidelli, 2009) initial size-frequency distribution that are consistent with observations reported in Gladman et al. (2009). Rotational disruption is a new mechanism that must be included in all future collisional evolution models of asteroids.Comment: 5 pages, 3 figures, accepted in MNRAS letter

Density functional theory in transition-metal chemistry: a self-consistent Hubbard U approach

Transition-metal centers are the active sites for many biological and inorganic chemical reactions. Notwithstanding this central importance, density-functional theory calculations based on generalized-gradient approximations often fail to describe energetics, multiplet structures, reaction barriers, and geometries around the active sites. We suggest here an alternative approach, derived from the Hubbard U correction to solid-state problems, that provides an excellent agreement with correlated-electron quantum chemistry calculations in test cases that range from the ground state of Fe$_2$ and Fe$_2^-$ to the addition-elimination of molecular hydrogen on FeO$^+$. The Hubbard U is determined with a novel self-consistent procedure based on a linear-response approach.Comment: 5 pages, 3 figures, Phys. Rev. Lett., in pres