Abstract:
SCF MS-Xα calculations of the electronic structure of diatomic copper(I) and silver(I) halides MX (M = Cu, Ag; X = F, Cl, Br, I) have been carried out to investigate the bonding and nuclear quadrupole coupling in these molecules. Reasonable agreement (to within 30%) is obtained between the calculated and observed halogen coupling constants. The agreement is rather poorer for the copper coupling constants, which are small in magnitude, since they result from near cancellation of large but opposing contributions from the copper 3d and 4p orbitals. However, the calculations reproduce the observed negative sign of the field gradient at the copper nucleus, as well as the observed decrease in the copper coupling constant from CuF to CuI. The reasons for this trend are discussed.