Density functional calculations of nuclear quadrupole coupling constants in the zero-order regular approximation for relativistic effects

The zeroth-order regular approximation (ZORA) is used for the evaluation of the electric field gradient, and hence nuclear quadrupole coupling constan ts, in some closed shell molecules. It is shown that for valence orbitals t he ZORA-4 electron density, which includes a small component density ("pict ure-change correction"), very accurately agrees with the Dirac electron den sity. For hydrogen-like atoms exact relations between the ZORA-4 and Dirac formalism are given for the calculation of the electric field gradient. Den sity functional (DFT) calculations of the electric field gradients for a nu mber of diatomic halides at the halogen nuclei Cl, Br, and I and at the met allic nuclei Al, Ga, In, Th, Cu, and Ag are presented. Scalar relativistic effects, spin-orbit effects, and the effects of picture-change correction, which introduces the small component density, are discussed. The results fo r the thallium halides show a large effect of spin-orbit coupling. Our ZORA -4 DFT calculations suggest adjustment of some of the nuclear quadrupole mo ments to Q(Br-79)=0.30(1) barn, Q(I-127)=-0.69(3) barn, and Q(In-115)=0.74( 3) barn, which should be checked by future highly correlated ab initio rela tivistic calculations. In the copper and silver halides the results with th e used gradient corrected density functional are not in good agreement with experiment. (C) 2000 American Institute of Physics. [S0021-9606(00)30517-7 ].