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Matildite Contact with Media: First-Principles Study of AgBiS2 Surfaces and Nanoparticle Morphology

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Motivated by the interest in AgBiS2 material for solar light harvesting applications, a detailed bulk first-principles quantum mechanical study of its surface properties is presented. Density functional theory based calculations with the Perdew-Burke-Ernzerhof functional have been carried out for different surface orientations and terminations of the matildite polymorph. From the results, two particularly stable facets are predicted to dominate Wulff shaped AgBiS2 nanoparticles. These are the (001) type nonpolar surface and the (111) polar terminations where facets are exposed containing solely Ag or S atoms. The Wulff equilibrium shape is predicted to be a cube with only two edges capped. This particular shape explains a previously reported surface enrichment of Ag with respect to Bi of ∼1.5. The (001) surfaces display an ionic character similar to bulk AgBiS2, with a low work function of 4.31 eV, although the inspection of the density of states (DOS) reveals a bandgap increased by 0.3 eV compared to bulk. This surface effect could explain the bulk wavelength overestimation of the absorption coefficient decay, as previously determined. Last but not least, the DOS of the (111) polar termination reveals a metallic character, where Fermi level is located below that on the (001) surfaces. Possible implications of the different electronic structure of these surfaces in the reported photoactivity are discussed.

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VIÑES SOLANA, Francesc, KONSTANTATOS, Gerasimos, ILLAS I RIERA, Francesc. Matildite Contact with Media: First-Principles Study of AgBiS2 Surfaces and Nanoparticle Morphology. _Journal of Physical Chemistry B_. 2017. Vol. 122, núm. 2, pàgs. 521-526. [consulta: 25 de febrer de 2026]. ISSN: 1520-6106. [Disponible a: https://hdl.handle.net/2445/128146]

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