Relevance of on-site and intersite Coulomb interactions in the Kitaev-Heisenberg magnet <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mrow> <mml:msub> <mml:mi>Na</mml:mi> <mml:mn>3</mml:mn> </mml:msub> <mml:msub> <mml:mi>Co</mml:mi> <mml:mn>2</mml:mn> </mml:msub> <mml:msub> <mml:mi>SbO</mml:mi> <mml:mn>6</mml:mn> </mml:msub> </mml:mrow> </mml:math>

The detection of considerable spin frustration in honeycomb cobalt oxide compounds indicates the presence of sizable Kitaev interactions in these systems, enlarging the pool of Kitaev spin liquid candidates. Several key questions remain to be answered, as basic as the mechanisms behind Kitaev couplings in Co 2 + t 2 g 5 e g 2 magnets. Analyzing the quantum chemistry of interacting magnetic moments in Na 3 Co 2 SbO 6 , a representative L S -coupled t 2 g 5 e g 2 oxide, we find that the Kitaev and off-diagonal Γ interactions are substantial and antiferromagnetic but somewhat weaker than the Heisenberg contribution. All nearest-neighbor couplings feature massive contributions from direct Coulomb exchange and/or on-site multiconfigurational dressing, mechanisms not considered so far in descriptive models of Kitaev-Heisenberg magnetism. These findings call for systematic wave function quantum chemical studies to understand direct-indirect exchange synergies in Kitaev-Heisenberg magnets and how to possibly tune intersite couplings toward the Kitaev spin liquid ground state.