Density Functional Theory (DFT) has emerged as the preferred method for the calculation of the electronic structure of medium to large size molecules involving lighter atoms. However, its application to compounds including heavier elements is less than straightforward. Because of effects like spin-orbit and the necessity of a proper relativistic treatment of both electron-nuclear and electron-electron interactions, an accurate description of the chemistry of heavy elements necessarily involves noncollinear spins. In this contribution we discuss the issues that arise when density functionals developed assuming collinear spins, are used in two and four-component formulations of DFT where noncollinear spins can be properly described. We discuss an extension of existing DFT functionals to the noncollinear regime [1,2] which has the correct invariance properties, affords a nonvanishing local magnetic torque and it is free of numerical instabilities.<br/><br/>[1] Scalmani, G.; Frisch, M. J., “A New Approach to Noncollinear Spin Density Functional Theory beyond the Local Density Approximation”, J. Chem. Theory Comput. 2012, 8 (7), 2193-2196; [2] Bulik, I. W.; Scalmani, G.; Frisch, M. J.; Scuseria, G. E., “Noncollinear density functional theory having proper invariance and local torque properties”, Phys. Rev. B 2013, 87 (3) 035117.

On the application of density functional theory to heavy elements: Density functionals for two- and four-component methods

251st National Meeting (2016)

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