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

Abstract

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.

arXiv comment6 pages, 5 figures, and supporting information

References in corpus (11)

• The GW method
• Frequency-dependent local interactions and low-energy effective models from electronic structure calculations
• Ab initio calculations of quasiparticle band structure in correlated systems: LDA++ approach
• First-principles Calculations of the Electronic Structure and Spectra of Strongly Correlated Systems: Dynamical Mean-field Theory
• Dynamical Mean-Field Theory within an Augmented Plane-Wave Framework: Assessing Electronic Correlations in the Iron Pnictide LaFeAsO
• Hubbard U and Hund's Exchange J in Transition Metal Oxides: Screening vs. Localization Trends from Constrained Random Phase Approximation
• Self-consistency over the charge-density in dynamical mean-field theory: a linear muffin-tin implementation and some physical implications
• Importance of electronic correlations for structural and magnetic properties of the iron pnictide superconductor LaFeAsO
• Optical properties of correlated materials -- Generalized Peierls approach and its application to VO2
• Optical Properties of Correlated Materials -- or Why Intelligent Windows may look Dirty
• Materials Design using Correlated Oxides: Optical Properties of Vanadium Dioxide

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