Many-body renormalization of forces in f-electron materials

Abstract

We present the implementation of dynamical mean-field theory (DMFT) in the CASTEP ab initio code. We explain in detail the theoretical framework for DFT+DMFT and we demonstrate our implementation for three strongly-correlated systems with f -shell electrons: γ -cerium, cerium sesquioxide Ce2O3, and samarium telluride SmTe by using a Hubbard I solver. We find very good agreement with previous benchmark DFT+DMFT calculations of cerium compounds, while for SmTe we show the improved agreement with the experimental structural parameters as compared with LDA. Our implementation works equally well for both norm-conserving and ultrasoft pseudopotentials, and we apply it to the calculation of total energy, bulk modulus, equilibrium volumes, and internal forces in the two cerium compounds. In Ce2O3 we report a dramatic reduction of the internal forces acting on coordinates not constrained by unit cell symmetries. This reduction is induced by the many-body effects, which can only be captured at the DMFT level. In addition, we derive an alternative form for treating the high-frequency tails of the Green function in Matsubara frequency summations. Our treatment allows a reduction in the bias when calculating the correlation energies and occupation matrices to high precision.