Spin-Orbit Natural Transition Orbitals and Spin-Forbidden Transitions

Natural transition orbitals (NTOs) are in widespread use for visualizing and analyzing electronic transitions. The present work introduces the analysis of formally spin-forbidden transitions with the help of complex-valued spin-orbit (SO) NTOs. The analysis specifically focuses on the components in such transitions that cause their intensity to be nonzero because of SO coupling. Transition properties such as transition dipole moments are partitioned into SO-NTO hole-particle pairs, such that contributions to the intensity from specific occupied and unoccupied orbitals are obtained. The method has been implemented within the restricted active space (RAS) self-consistent field wave function theory framework, with SO coupling treated by RAS state interaction. SO-NTOs have a broad range of potential applications, which is illustrated by the T-2-S-1 state mixing in pyrazine, spin-forbidden versus spin-allowed 4f-5d transitions in the Tb3+ ion, and the phosphorescence of tris(2-phenylpyridine) iridium [Ir(PPY)(3)].