| Abstract
| - Magnetic, vibrational, and optical techniques are combined with density functional calculationsto elucidate the electronic structure of the diamagnetic mononuclear side-on CuII-superoxo complex. Theelectronic nature of its lowest singlet/triplet states and the ground-state diamagnetism are explored. Thetriplet state is found to involve the interaction between the Cu xy and the superoxideorbitals, which areorthogonal to each other. The singlet ground state involves the interaction between the Cu xy and thein-plane superoxideorbitals, which have a large overlap and thus strong bonding. The ground-statesinglet/triplet states are therefore fundamentally different in orbital origin and not appropriately describedby an exchange model. The ground-state singlet is highly delocalized with no spin polarization.
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