Core spin-polarization correction in pseudopotential-based electronic structure calculations

A simple scheme for the evaluation of the core spin-polarization contribution within pseudopotential electronic structure methods is proposed. The method uses a reconstruction of the all-electron wave functions and the frozen valence spin-density approximation to solve the Kohn-Sham equations for core electrons only. The core contribution to the spin-density at the point of the nucleus corrects for the leading error in the Fermi contact hyperfine coupling constants within pseudopotential-based electronic structure calculations. The correction is implemented in the framework of pseudopotential plane-wave density functional theory. Comparison with all-electron Slater-type orbital calculations on a number of molecular radicals containing first-row elements proves the accuracy of this approach.

Figure 1

The contributions to the ${\rho }^s\left(r\right)$ in spin-polarized nitrogen atom.