Descripción: 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 ε0. 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. © 2006 American Institute of Physics.

Descripción: Continuum solvent models have become a standard technique in the context of electronic structure calculations, yet no implementations have been reported capable to perform molecular dynamics at solid-liquid interfaces. We propose here such a continuum approach in a density functional theory framework using plane-wave basis sets and periodic boundary conditions. Our work stems from a recent model designed for Car-Parrinello simulations of quantum solutes in a dielectric medium [D. A. Scherlis, J. Chem. Phys. 124, 074103 (2006)], for which the permittivity of the solvent is defined as a function of the electronic density of the solute. This strategy turns out to be inadequate for systems extended in two dimensions: the dependence of the dielectric function on the electronic density introduces a new term in the Kohn-Sham potential, which becomes unphysically large at the interfacial region, seriously affecting the convergence of the self-consistent calculations. If the dielectric medium is properly redefined as a function of the atomic coordinates, a good convergence is obtained and the constant of motion is conserved during the molecular dynamics simulations. The Poisson problem is solved using a multigrid method, and in this way Car-Parrinello molecular dynamics simulations of solid-liquid interfaces can be performed at a very moderate computational cost. This scheme is employed to investigate the acid-base equilibrium at the TiO2 -water interface. The aqueous behavior of titania surfaces has stimulated a large amount of experimental research, but many open questions remain concerning the molecular mechanisms determining the chemistry of the interface. Here we make an attempt to answer some of them, putting to the test our continuum model. © 2009 American Institute of Physics.

Descripción: Theoretical, computational, and experimental studies have converged to a model of decision-making in which sensory evidence is stochastically integrated to a threshold, implementing a shift from an analog to a discrete form of computation. Understanding how this process can be chained and sequenced - as virtually all real-life tasks involve a sequence of decisions - remains an open question in neuroscience. We reasoned that incorporating a virtual continuum of possible behavioral outcomes in a simple decision task - a fundamental ingredient of real-life decision-making - should result in a progressive sequential approximation to the correct response. We used real-time tracking of motor action in a decision task, as a measure of cognitive states reflecting an internal decision process. We found that response trajectories were spontaneously segmented into a discrete sequence of explorations separated by brief stops (about 200ms) - which remained unconscious to the participants. The characteristics of these stops were indicative of a decision process - a "moment of thought": their duration correlated with the difficulty of the decision and with the efficiency of the subsequent exploration. Our findings suggest that simple navigation in an abstract space involves a discrete sequence of explorations and stops and, moreover, that these stops reveal a fingerprint of moments of thought. © 2011 Graziano, Polosecki, Shalom and Sigman.