The electronic structure of the neutral and cationic pentaatomic silver bare clusters is investigated by the Dirac scattered-wave (DSW) method. The results indicate that there is significant 5s1/2-4d5/2 hybridization in the bonding molecular orbitals, due to relativistic effects. Molecular hyperfine interactions (hfi) are calculated for the paramagnetic species Ag5q+ (q = 0, 2, and 4) through a first-order perturbation to the Dirac Hamiltonian. The ground state (2E′) orbital degeneracy of Ag5 in D3h geometry is removed by spin-orbit interaction leading to Kramers degeneracy, and consequently the D3h geometry of Ag5 will not distort due to Jahn-Teller effect. It is found that the hyperfine coupling constants calculated by using a four-component wave function for the Ag52+ and Ag 54+ clusters differ significantly from previously computed hfi using a second-order perturbation to the Schrödinger Hamiltonian. First ionization potentials and excitation energies are predicted for all the species as calculated by the spin-restricted transition state method.
|Number of pages||13|
|Journal||The Journal of Chemical Physics|
|Publication status||Published - 1986|
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry