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All-electron density functional calculations for electron and nuclear spin interactions in molecules and solids

MetadataDetails
Publication Date2019-04-04
JournalPhysical Review Materials
AuthorsKrishnendu Ghosh, He Ma, Vikram Gavini, Giulia Galli, Krishnendu Ghosh
InstitutionsUniversity of Chicago, University of Michigan–Ann Arbor
Citations25

The interaction between electronic and nuclear spins in the presence of external magnetic fields can be described by a spin Hamiltonian, with parameters obtained from first principles, electronic structure calculations. We describe an approach to compute these parameters, applicable to both molecules and solids, which is based on density functional theory (DFT) and real-space, all-electron calculations using finite elements (FE). We report results for hyperfine tensors, zero field splitting tensors (spin-spin component), and nuclear quadrupole tensors of a series of molecules and of the nitrogen-vacancy center in diamond. We compare our results with calculations using Gaussian orbitals and plane-wave basis sets, and we discuss their numerical accuracy. Furthermore, we show that calculations based on FE can be systematically converged with respect to the basis set, thus allowing one to establish reference values for the spin Hamiltonian parameters, at a given level of DFT.

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