Molecular hyperfine interactions in Ag(CO)3

Abstract

Relativistic molecular orbital calculations in the multiple scattering approximation are reported for silver tricarbonyl, and comparisons are made to optical absorption and electron spin resonance spectra. Spin–orbit effects are modelled through the Dirac scattered-wave (DSW) formalism. Spin–polarization effects are estimated from quasirelativistic spin-unrestricted calculations. The influence of different local density potentials on the spin distributions and hyperfine tensors are examined. The calculations show good agreement with optical spectral data and with the observed 107Ag and 13C hyperfine tensors. The use of relativistic exchange–correlation potentials in calculating spin-dependent properties leads to a slightly better agreement with experiment. The calculations predict that the unpaired electron in Ag(CO)3 has about 40% silver 5pz character.