A first-principles characterization of the structure and electronic structure of $α$-S and Rh-S chalcogenides

Physics – Condensed Matter – Materials Science

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10.1103/PhysRevB.80.214115

We have used first-principles calculations to study the structural, electronic, and thermodynamic properties of the three known forms of Rh-S chalcogenides: Rh$_2$S$_3$, Rh$_3$S$_4$, and Rh$_{17}$S$_{15}$. Only the first of these materials of interest for catalysis had been studied previously within this approach. We find that Rh$_{17}$S$_{15}$ crystallizes in a {\em Pm}\={3}{\em m} centrosymmetric structure, as believed experimentally but never confirmed. We show band structures and densities of states for these compounds. Finally, we also investigated the ground state structure of solid sulfur ($\alpha$-S), one of the few elements that represents a challenge for full first-principles calculations due to its demanding 128-atom unit cell and dispersion interactionis between S$_8$ units.

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