Density-functional approach to the valence change in SmS: Normal and high-pressure phases

Abstract

The electronic structure of SmS in dependence of the lattice constant is calculated by means of density-functional theory. The local-density approximation (LDA) to the exchange and correlation potential is employed. The 4f electrons, however, are treated in three different ways, viz., (i) as localized core states, (ii) as extended band states, and (iii) as self-interaction corrected (SIC) band states. While the experimentally observed Sm valency of normal state SmS (black phase) cannot be described by methods (i) and (ii) the SIC calculations are consistent with the measured value. For pressures above 30 kbar, method (ii) agrees well with the observed Sm valency, whereas methods (i) and (iii) fail. Therefore we conclude that the phase transition in SmS is very similar to the \ensuremath{\alpha}-\ensuremath{\gamma} transition in Ce metal. The SIC band structure shows the splitting between the occupied and empty 4f states due to the large on-site electron correlation. The Fermi level ${\mathrm{\ensuremath{\epsilon}}}_{\mathit{F}}$ is situated in the gap between the S 3p states and the Sm band states mainly of 5d character. In the high-pressure phase the 4f states presumably become delocalized, resulting in vanishing self-interaction corrections. Therefore the uncorrected LDA results are appropriate for the high-pressure phase.