Correlated ab-initio calculations for ground-state properties of II-VI semiconductors

TL;DR

This paper performs advanced correlated ab-initio calculations on six II-VI semiconductors, accurately predicting their cohesive energies, lattice constants, and bulk moduli by incorporating relativistic pseudopotentials and bond correlation schemes.

Contribution

It introduces a comprehensive correlated calculation method using an incremental scheme and relativistic pseudopotentials for II-VI semiconductors, improving prediction accuracy of ground-state properties.

Findings

Recovered about 94% of experimental cohesive energies.

Predicted lattice constants within ~1% accuracy.

Bulk moduli are on average 10% higher than experimental values.

Abstract

Correlated ab-initio ground-state calculations, using relativistic energy-consistent pseudopotentials, are performed for six II-VI semiconductors. Valence ($ns,np$) correlations are evaluated using the coupled cluster approach with single and double excitations. An incremental scheme is applied based on correlation contributions of localized bond orbitals and of pairs and triples of such bonds. In view of the high polarity of the bonds in II-VI compounds, we examine both, ionic and covalent embedding schemes for the calculation of individual bond increments. Also, a partitioning of the correlation energy according to local ionic increments is tested. Core-valence ($nsp,(n-1)d$) correlation effects are taken into account via a core-polarization potential. Combining the results at the correlated level with corresponding Hartree-Fock data we recover about 94% of the experimental cohesive energies; lattice constants are accurate to \sim 1%; bulk moduli are on average 10% too large compared with experiment.