Electron-spin magnetic moments of the 2Σ+ ions Li2+, Li2−, and Be2+: An ab initio ROHF study

For the ²Σ⁺ ground states of the ions Li₂⁺, Li₂⁻, and Be₂⁺, the dependence of the magnetic moment (parametrized by g-shifts) on the bond length R was studied at the ROHF level. The Δ g-values were calculated via a perturbative approach (complete to second order in Breit-Pauli interactions) using quadruple-zeta AO basis sets augmented by semidiffuse and polarization functions. All Δ g-values in these systems are negative. The parallel component Δ g_∥ generally changes little with R, remaining close to the g-shift of the corresponding ²S atomic dissociation product. For Li₂⁺ and Be₂⁺, the perpendicular component Δ g _⟂ is more sensitive to geometry than is Δ g_∥, mainly because of the second-order magnetic coupling with excited ²Π states. For Li₂⁻, Δ g _⟂ and Δ g_∥ are similar due to the large size of the 2σ_u, SOMO, resulting in g-values close to that of a free electron. © 1997 John Wiley & Sons, Inc. Int J Quant Chem 63: 511–521, 1997