Abstract

We present relativistic and non-relativistic ab initio treatments of the hexafluorides of group 10 metals. Non-relativistic equilibrium geometries belong to the D 4 h point group while relativistic calculations afford O h geometries. Relativistic effects yield singlet ground states for all complexes, the stabilization energy coming from the spin-orbit coupling. We used Time Dependent Density Functional Theory at the ZORA two component Regular Approximation to calculate the excitation spectra of the complexes. The predicted spectra correctly reproduce the experimental results. Relativistic effects in conjunction with spin-orbit coupling stabilize the O h geometry and are important in the prediction of spectra and properties of the hexafluorides of the group 10 metals. © 2008 Elsevier B.V. All rights reserved.