title: Real-time simulations of photoinduced coherent charge transfer and proton-coupled electron transfer.
abstract: Photoinduced electron transfer (ET) and proton-coupled electron transfer (PCET) are fundamental processes in natural phenomena, most noticeably in photosynthesis. Time-resolved spectroscopic evidence of coherent oscillatory behavior associated with these processes has been reported both in complex biological environments, as well as in biomimetic models for artificial photosynthesis. Here, we consider a few biomimetic models to investigate these processes in real-time simulations based on ab initio molecular dynamics and Ehrenfest dynamics. This allows for a detailed analysis on how photon-to-charge conversion is promoted by a coupling of the electronic excitation with specific vibrational modes and with proton displacements. The ET process shows a characteristic coherence that is linked to the nuclear motion at the interface between donor and acceptor. We also show real-time evidence of PCET in a benzimidazole-phenol redox relay.
authors.affiliation: Leiden Institute of Chemistry, Leiden University, Einsteinweg 55, 2300 RA Leiden (The Netherlands).
authors.forename: Thomas J
authors.initials: TJ
authors.lastname: Eisenmayer
authors.forename: Francesco
authors.initials: F
authors.lastname: Buda
mesh_terms: D001562:Benzimidazoles / Q000737:chemistry*; D004579:Electron Transport; D004583:Electrons; D008027:Light; D056004:Molecular Dynamics Simulation; D010084:Oxidation-Reduction; D019800:Phenol / Q000737:chemistry*; D011522:Protons; D011789:Quantum Theory; D014227:Triazines / Q000737:chemistry
chemical_list: D001562:Benzimidazoles; D011522:Protons; D014227:Triazines; D019800:Phenol; C031000:benzimidazole; C011907:melamine
keywords: Ehrenfest dynamics; coherence; electron transfer; molecular dynamics; proton-coupled electron transfer