The electronic structure of AuF 6 may be different from the others. AuF 6 has ungerade-type orbitals with higher energies than t 2g -type orbitals, as shown in Figure of the Supporting information. AuF 6 should not be explained like the other third-row transition metal fluorides. More careful investigation of the reference orbitals and active spaces is required, and thus, we do not study AuF 6 in the subsequent sections. The bond length of AuF 6 shown in Table V is different from the literature value, but we also found a local minimum of AuF 6 that is closer to the literature value (1.913 Å (×2) and 1.898 Å(×4) at the SF-X2C/MRCI/dyall.v3z level), which is 6354 cm -1 less stable than the one shown in Table .