Simulation of Ultrafast Excited-State Dynamics in Fe(II) Complexes: Assessment of Electronic Structure Descriptions

The assessment of electronic structure descriptions utilized in the simulation of the ultrafast excited-state dynamics of Fe(II) complexes is presented. Herein, we evaluate the performance of the RPBE, OPBE, BLYP, B3LYP, B3LYP*, PBE0, TPSSh, CAM-B3LYP, and LC-BLYP (time-dependent) density functional theory (DFT/TD-DFT) methods in full-dimensional trajectory surface hopping (TSH) simulations carried out on linear vibronic coupling (LVC) potentials. We exploit the existence of time-resolved X-ray emission spectroscopy (XES) data for the [Fe(bmip)2]2+ and [Fe(terpy)2]2+ prototypes for dynamics between metal-to-ligand charge-transfer (MLCT) and metal-centered (MC) states, which serve as a reference to benchmark the calculations (bmip = 2,6-bis(3-methyl-imidazole-1-ylidine)-pyridine, terpy = 2,2′:6′,2″-terpyridine). The results show that the simulated ultrafast population dynamics between MLCT and MC states with various spin multiplicities (singlet, triplet, and quintet) highly depend on the utilized DFT/TD-DFT method, with the percentage of exact (Hartree–Fock) exchange being the governing factor. Importantly, B3LYP* and TPSSh are the only DFT/TD-DFT methods with satisfactory performance, best reproducing the experimentally resolved dynamics for both complexes, signaling an optimal balance in the description of MLCT–MC energetics. This work demonstrates the power of combining TSH/LVC dynamics simulations with time-resolved experimental reference data to benchmark full-dimensional potential energy surfaces.