Rare-Earth vs. Heavy Metal Pigments and their Colors from First Principles

Many inorganic pigments contain heavy metals hazardous to health and environment. Much attention has been devoted to the quest for non-toxic alternatives based on rare-earth elements. The computation of colors from first principles is a challenge to electronic structure methods however, especially for materials with localized f-orbitals. Here, starting from atomic positions only, we compute the color of the red pigment cerium fluorosulfide CeSF, as well as of mercury sulfide HgS (classic vermilion). Our methodology employs many-body theories to compute the optical absorption, combined with an intermediate length-scale modelization to assess how coloration depends on film thickness, pigment concentration and granularity. We introduce a quantitative criterion for the performance of a pigment. While for HgS this criterion is satisfied due to large transition matrix elements between wide bands, CeSF presents an alternative paradigm: the bright red color is shown to stem from the combined effect of the quasi two-dimensionality and the localized nature of 4f-states. Our work demonstrates the power of modern computational methods, with implications for the theoretical design of materials with specific optical properties.

Low-energy models for correlated materials: bandwidth renormalization from Coulombic screening

We provide a prescription for constructing Hamiltonians representing the low energy physics of correlated electron materials with dynamically screened Coulomb interactions. The key feature is a renormalization of the hopping and hybridization parameters by the processes that lead to the dynamical screening. The renormalization is shown to be non-negligible for various classes of correlated electron materials. The bandwidth reduction effect is necessary for connecting models to materials behavior and for making quantitative predictions for low-energy properties of solids.

Spectral density of an interacting dot coupled indirectly to conducting leads

We study the spectral density of electrons rho in an interacting quantum dot (QD) with a hybridization lambda to a non-interacting QD, which in turn is coupled to a non-interacting conduction band. The system corresponds to an impurity Anderson model in which the conduction band has a Lorentzian density of states of width Delta2. We solved the model using perturbation theory in the Coulomb repulsion U (PTU) up to second order and a slave-boson mean-field approximation (SBMFA). The PTU works surprisingly well near the exactly solvable limit Delta2 -> 0. For fixed U and large enough lambda or small enough Delta2, the Kondo peak in rho(omega) splits into two peaks. This splitting can be understood in terms of weakly interacting quasiparticles. Before the splitting takes place the universal properties of the model in the Kondo regime are lost. Using the SBMFA, simple analytical expressions for the occurrence of split peaks are obtained. For small or moderate Delta2, the side bands of rho(omega) have the form of narrow resonances, that were missed in previous studies using the numerical renormalization group. This technique also has shortcomings for describing properly the split Kondo peaks. As the temperature is increased, the intensity of the split Kondo peaks decreases, but it is not completely suppressed at high temperatures.