Abstract
The alkali hyperfine structure (hfs) splittings in the 2Σ radicals RbO and CsO are analyzed using a semiempirical valence bond (VB) wave function similar to that used previously for the noble gas monohalides. For the alkali monoxides this wave function is ψ=N(2Σ)[χ𝒜Φ(M+ ⋅ ⋅ ⋅ O−) +(1−χ2)1/2𝒜Φ(M++ ⋅ ⋅ ⋅ O=)], where M and O denote the alkali and oxygen, respectively, and 𝒜 is the antisymmetrization operator. This antisymmetrization and the effects of interatomic electron correlation in the Φ(M++ ⋅ ⋅ ⋅ O=) VB structure are the principal contributors to the hfs. At the bond distances RRbO=4.30 and RCsO=4.67a0 the parameters χ=0.9996 and 0.9967 for RbO and CsO, respectively, give good agreement between theory and experiment for both the isotropic and anisotropic hfs. The admixture of the doubly ionized Φ(M++ ⋅ ⋅ ⋅ O=) VB structure, which produces covalent bonding involving the alkali cation core orbitals and the oxygen anion valence orbitals, is small as expected from the high energy of this structure.
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