Fast Intersystem Crossing in Transition-Metal Complexes

Abstract

The mechanism behind fast intersystem crossing in transition-metal complexes is shown to be a result of the dephasing of the photoexcited state to the phonon continuum of a different state with a significantly different transition metal-ligand distance. The coupling is a result of the spin-orbit interaction causing a change in the local moment. Recurrence to the initial state is prevented by the damping of the phonon oscillation. The decay time is faster than the oscillation frequency of the transition metal-ligand stretch mode, in agreement with experiment. For energies above the region where the strongest coupling occurs, a slower "leakage-type" decay is observed. If the photoexcited state is lower in energy than the state it couples to, then there is no decay.

5 pages, 3 figures, accepted for publication in Phys.Rev.Lett

Cited by in corpus (4)

• Non-adiabatic quantum dynamics without potential energy surfaces based on second-quantized electrons: application within the framework of the MCTDH method
• Model of ultrafast demagnetization driven by spin-orbit coupling in a photoexcited antiferromagnetic insulator Cr2O3
• Model of Nonadiabatic to Adiabatic Dynamical Quantum Phase Transition in Photoexcited Systems
• Universal Anomaly of Dynamics at Phase Transition Points Induced by Pancharatnam-Berry Phase