Abstract
In this study, we investigated theoretically the Mott-insulating phase of a deficient spinel chalcogenide , which is known to form a tetrahedral cluster unit that results in molecular orbitals (MOs) with a narrow bandwidth in the noninteracting limit. We used a cluster extension of charge self-consistent embedded dynamical mean-field theory to study the impact of strong intracluster correlations on the spectral properties as well as the structural degrees of freedom of the system. We found that the strong tetrahedral clustering renders the atomic Mott picture ineffective, and that the resulting MO picture is essential to describe the Mott phase. It was also found that, while the spectral properties can be qualitatively described by the truncation of the Hilbert space down to the lowest-energy MO, a proper description of the structural degrees of freedom requires the inclusion of multi-MO correlations that span a larger energy window. Specifically, we found that the lowest-energy MO description overemphasizes the clustering tendency, while the inclusion of the Hund's coupling between the lower- and higher-energy MOs corrects this tendency, bringing the theoretically predicted crystal structure into good agreement with the experiment.
- Received 22 October 2018
- Revised 24 February 2020
- Accepted 24 July 2020
DOI:https://doi.org/10.1103/PhysRevB.102.081105
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