Calculation of exchange couplings in the electronically excited state of molecular three-spin systems.

Photogenerated molecular three-spin systems, composed of a chromophore and a covalently bound stable radical, are promising candidates for applications in the field of molecular spintronics. Through excitation with light, an excited doublet state and a quartet state are generated, whereby their energy difference depends on the exchange interaction between the chromophore triplet state (T) and the stable radical (R). In order to establish design rules for new materials to be used in molecular spintronics devices, it is of great importance to gain knowledge on the magnitude of as well as the factors influencing on a molecular level. Here, we present a robust and reliable computational method to determine excited state exchange couplings in three-electron-three-centre systems based on a CASSCF/QD-NEVPT2 approach. The methodology is benchmarked and then applied to a series of molecules composed of a perylene chromophore covalently linked to various stable radicals. We calculate the phenomenological exchange interaction between chromophore and radical, which can be compared directly to the experiment, but also illustrate how the individual exchange interactions can be extracted using an effective Hamiltonian that corresponds to the Heisenberg-Dirac-Van-Vleck Hamiltonian. The latter procedure enables a more detailed analysis of the contributions to the exchange interaction and yields additional insight that will be invaluable for future design optimisation.