⁶³Cu and ¹⁹⁷Au nuclear quadrupole moments from four-component relativistic density-functional calculations using correct long-range exchange

The electric field gradient in late transition metal compounds is incorrectly determined by most density functionals. We show that the coupling of short-range density functional based with long-range wave function based methods using a reparametrization of the Coulomb-attenuated Becke three-parameter Lee-Yang-Parr approximation gives reliable results for the electric field gradients of copper and gold for a series of compounds. This results in nuclear quadrupole moments of −0.208 b for ⁶³Cu and +0.526 b for ¹⁹⁷Au in good agreement with experimental values of −0.220(15) and +0.547(16)b, respectively.