*Phys Rev Lett ; 122(8): 086601, 2019 Mar 01.*

##### RESUMO

The electrical σ and thermal conductivity λ of liquid iron are calculated with spin-polarized density-functional-theory-based simulations over a significant pressure and temperature range using the Kubo-Greenwood formalism. We show that a paramagnetic state is stable in the liquid up to high temperatures at ambient pressure and that the discrepancy between experimental results and spin-degenerate simulations for σ and λ of more than 30% are reduced to within 10% with lower values resulting from the spin-polarized simulations. Along the 3700 K isotherm, we explore the persistence of magnetic fluctuations toward high densities, and beyond 20-50 GPa the liquid becomes diamagnetic, which suggests the existence of a continuous paramagnetic-to-diamagnetic transition. This transition exerts a significant influence on the physical properties of liquid iron, especially on σ and λ, and is potentially of high relevance for dynamo processes in Mercury and Mars.

*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.

*Proc Natl Acad Sci U S A ; 109(11): 4070-3, 2012 Mar 13.*

##### RESUMO

Earth's magnetic field is sustained by magnetohydrodynamic convection within the metallic liquid core. In a thermally advecting core, the fraction of heat available to drive the geodynamo is reduced by heat conducted along the core geotherm, which depends sensitively on the thermal conductivity of liquid iron and its alloys with candidate light elements. The thermal conductivity for Earth's core is very poorly constrained, with current estimates based on a set of scaling relations that were not previously tested at high pressures. We perform first-principles electronic structure computations to determine the thermal conductivity and electrical resistivity for Fe, Fe-Si, and Fe-O liquid alloys. Computed resistivity agrees very well with existing shock compression measurements and shows strong dependence on light element concentration and type. Thermal conductivity at pressure and temperature conditions characteristic of Earth's core is higher than previous extrapolations. Conductive heat flux near the core-mantle boundary is comparable to estimates of the total heat flux from the core but decreases with depth, so that thermally driven flow would be constrained to greater depths in the absence of an inner core.

*J Phys Condens Matter ; 22(29): 295501, 2010 Jul 28.*

##### RESUMO

A new study on the pressure-induced phase transitions of TiO(2) has been performed using all-electron density-functional theory based computations with the projector augmented wave and the linearized augmented plane wave methods considering five experimentally observed structures. The static results yield a picture that is consistent with experiments, i.e., phase transitions with pressure are predicted as rutile --> monoclinic baddeleyite (MI) --> orthorhombic I (OI) --> cotunnite (OII) on compression, and OII --> OI --> MI --> columbite (TiO(2)II) on decompression. The elasticities of these five polymorphs are compared. Except for the baddeleyite structure, which is considerably softer than the other polymorphs, all phases show a zero pressure bulk modulus in the range of 200-240 GPa, consistent with compression results and the single crystal elastic constant; on the basis of these results we can say that the cotunnite phase is not a superhard TiO(2) polymorph as has been suggested previously. We further find that the rutile and columbite structures are energetically very similar, with the columbite structure favored slightly. All polymorphs are predicted as insulating with comparable band gaps (â¼1.7-2.3 eV). Crystal field splitting for the Ti 3d electronic states leads to two distinct conduction bands in rutile and TiO(2)II for energies smaller than 8 eV, while there is a single conduction band for the other high pressure structures.

*Proc Natl Acad Sci U S A ; 101(1): 33-6, 2004 Jan 06.*

##### RESUMO

The magnetic state of hexagonal close-packed iron has been the subject of debate for more than three decades. Although Mössbauer measurements find no evidence of the hyperfine splitting that can signal the presence of magnetic moments, density functional theory predicts an antiferromagnetic (afm) ground state. This discrepancy between theory and experiment is now particularly important because of recent experimental findings of anomalous splitting in the Raman spectra and the presence of superconductivity in hexagonal close-packed iron, which may be caused by magnetic correlations. Here, we report results from first principles calculations on the previously predicted theoretical collinear afm ground state that strongly support the presence of afm correlations in hexagonal close-packed iron. We show that anomalous splitting of the Raman mode can be explained by spin-phonon interactions. Moreover, we find that the calculated hyperfine field is very weak and would lead to hyperfine splitting below the resolution of Mössbauer experiments.