Electronic ground state and wavefunctions for scandium monoxide

Abstract:

Approximate wavefunctions for ScO have been calculated by the method of Roothaan to establish the ground-state assignment of the molecule. Experimental analysis leads to a 4∑ ground state, but this assignment has been questioned. The wavefunctions have been calculated with a limited basis in the matrix Hartree-Fock approximation at three internuclear distances about the minimum in the binding-energy curve. Basis functions of Slater type were selected to include effects of distortion and polarization. Preliminary and final calculations at every stage of computation yielded a 2∑ + ground state of configuration which is largely σ 2π4σ. No other states were found to be near degenerate with this in the region of equilibrium separation reported for the experimental 4∑ ground state. It is concluded from this and discussions of possible refinements to the present calculations that 2∑+ is the ground state of the molecule. It seems reasonable that the observed band structure can be explained as arising from a 2∑+ ground state with a large hyperfine splitting, possibly owing to the fact that at equilibrium separation ScO is approximately Sc2+(4s2S)O2- (1S). Ground-state parameters calculated here are De≥6.5 eV, re = 1.615 Å, ωe = 1373 cm-1, compared with the experimental values De = 6.9 eV, re = 1.668 Å, ωe = 971.55 cm-1 reported for the apparent 4∑ state.

Año de publicación:

1965

Keywords:

Fuente:

scopus