Revisiting the Electronic Structure of Cobalt Porphyrin Nitrene and Carbene Radicals with NEVPT2-CASSCF Calculations: Doublet versus Quartet Ground States
Nicolaas P. van Leest, Bas de Bruin
Abstract
) spin ground state, with a thermally accesible multireference and multideterminant "broken-symmetry" doublet spin excited state. A spin flip on the porphyrin-centered unpaired electron allows for interconversion between the quartet and broken-symmetry doublet spin states, with an approximate 10-fold higher Boltzmann population of the quartet at room temperature.
Topics & Concepts
ChemistryCarbeneNitrenePorphyrinGround stateUnpaired electronDensity functional theoryComplete active spacePhotochemistryRadicalComputational chemistryAtomic physicsCatalysisBasis setPhysicsBiochemistryOrganic chemistryMetal-Catalyzed Oxygenation MechanismsCyclopropane Reaction MechanismsMagnetism in coordination complexes