Theoretical study on electronic structures of AuF6 and its anions

Abstract
SCF–MO and CI calculations are carried out for AuFq6 (q=0, 1, 2, and 3) using a model potential method in which the major relativistic effects are incorporated. The calculated electron affinity of AuF6 is 9.56 eV, which is very close to Bartlett’s estimation of 10±0.5 eV. The calculated values for the equilibrium Au–F distance and the totally symmetric vibrational frequency of AuF6 agree well with experimental ones. The AuF6 anion has the lowest minimum energy in the AuFq6 (q=0, 1, 2, and 3) sequence, and the AuF3−6 anion is higher in energy by ∼4 eV than AuF6 and AuF2−6 at their equilibrium positions. The effects of adding a d‐type polarization function on F and an f‐type polarization function on Au are discussed.