Limitations of unconstrained LSDA+U calculations in predicting the electronic and magnetic ground state of a geometrically frustrated ZnV2O4 compound

Abstract

In the present work, we investigate the applicability of the LSDA+U method in understanding the electronic and magnetic properties of a geometrically frustrated ZnV2O4 compound, where the delicate balance of electrons, lattice, orbital and spin interactions play an important role in deciding its physical properties. In the ferromagnetic solution of the compound, only one type of orbital solution is found to exist in all ranges of U studied here. However, in antiferromagnetic (AFM) phase, two types of orbital solutions, AFM(OS1) and AFM(OS2), exist for U>3eV. If the difference of the electronic occupancy of dxz and dyz orbitals is less than 0.25, then AFM(OS1) solution is stabilized, whereas for higher values AFM(OS2) solution is stabilized. The use of unconstrained calculations within the fully localized double counting scheme is unable to predict the AFM ground state for U≤3eV. Our results clearly suggest the importance of constrained calculations in understanding the electronic and magnetic properties of a compound, where various competing interactions are present. In the AFM solution, the orbital ground state of the compound changes with varying U, where AFM(OS1) is found to be the ground state for U≤3eV and for higher values of U, AFM(OS2) is the ground state. The analysis of the band gap suggests that the AFM(OS2) is the real ground state of the compound.