Implementation of a Density Functional Theory-Based Method for the Calculation of the Hyperfine A-tensor in Periodic Systems with the Use of Numerical and Slater Type Atomic Orbitals: Application to Paramagnetic Defects

Abstract

The A-tensor parameterizes the "hyperfine" interaction of an "effective" electronic spin with the magnetic field due to the nuclear spin as monitored in an electron paramagnetic resonance (EPR) experiment. In this account, we describe an implementation for the calculation of the A-tensor in systems with translational invariance based on the Kohn-Sham form of density functional theory (KS DFT). The method is implemented in the periodic program BAND, where the Bloch states are expanded in the basis of numerical and Slater-type atomic orbitals (NAOs/STOs). This basis is well-suited for the accurate representation of the electron density near the nuclei, a prerequisite for the calculation of highly accurate hyperfine parameters. Our implementation does not rely on the frozen core approximation tacitly assumed in the pseudopotential schemes. The implementation is validated by performing calculations on the A-tensor for small atoms and molecules within the supercell approach as well as for paramagnetic defects in solids. In particular, we consider the A-tensor of "normal" and "anomalous" muonium defects in diamond and of the hydrogen cyanide anion radical HCN(-) in a KCl host crystal lattice.