*Phys Rev Lett ; 116(18): 186401, 2016 May 06.*

##### RESUMO

Charge carrier localization in extended atomic systems has been described previously as being driven by disorder, point defects, or distortions of the ionic lattice. Here we show for the first time by means of first-principles computations that charge carriers can spontaneously localize due to a purely electronic effect in otherwise perfectly ordered structures. Optimally tuned range-separated density functional theory and many-body perturbation calculations within the GW approximation reveal that in trans-polyacetylene and polythiophene the hole density localizes on a length scale of several nanometers. This is due to exchange-induced translational symmetry breaking of the charge density. Ionization potentials, optical absorption peaks, excitonic binding energies, and the optimally tuned range parameter itself all become independent of polymer length as it exceeds the critical localization length. Moreover, we find that lattice disorder and the formation of a polaron result from the charge localization in contrast to the traditional view that lattice distortions precede charge localization. Our results can explain experimental findings that polarons in conjugated polymers form instantaneously after exposure to ultrafast light pulses.

*J Chem Phys ; 142(3): 034107, 2015 Jan 21.*

##### RESUMO

In exact density functional theory, the total ground-state energy is a series of linear segments between integer electron points, a condition known as "piecewise linearity." Deviation from this condition is indicative of poor predictive capabilities for electronic structure, in particular of ionization energies, fundamental gaps, and charge transfer. In this article, we take a new look at the deviation from linearity (i.e., curvature) in the solid-state limit by considering two different ways of approaching it: a large finite system of increasing size and a crystal represented by an increasingly large reference cell with periodic boundary conditions. We show that the curvature approaches vanishing values in both limits, even for functionals which yield poor predictions of electronic structure, and therefore cannot be used as a diagnostic or constructive tool in solids. We find that the approach towards zero curvature is different in each of the two limits, owing to the presence of a compensating background charge in the periodic case. Based on these findings, we present a new criterion for functional construction and evaluation, derived from the size-dependence of the curvature, along with a practical method for evaluating this criterion. For large finite systems, we further show that the curvature is dominated by the self-interaction of the highest occupied eigenstate. These findings are illustrated by computational studies of various solids, semiconductor nanocrystals, and long alkane chains.

*Phys Chem Chem Phys ; 11(22): 4674-80, 2009 Jun 14.*

##### RESUMO

We developed a method for calculating the ground-state properties and fundamental band-gaps of solids, using a generalized Kohn-Sham approach combining a local density approximation (LDA) functional with a long-range explicit exchange orbital functional. We found that when the range parameter is selected according to the formula gamma=A/(epsiloninfinity-epsilon) where epsiloninfinity is the optical dielectric constant of the solid and epsilon=0.84 and A=0.216 a0(-1), predictions of the fundamental band-gap close to the experimental values are obtained for a variety of solids of different types. For most solids the range parameter gamma is small (i.e. explicit exchange is needed only at long distances) so the predicted values for lattice constants and bulk moduli are similar to those based on conventional LDA calculations. Preliminary calculations on silicon give a general band structure in good agreement with experiment.