Publications Repository - Gdańsk University of Technology

Time-dependent density functional theory calcula- tions combinedwith the Marcus theory of electron transfer (ET) were app lied on the molecular photocatalys t [(tbbpy) 2 Ru(tpph z)PdC l 2 ] 2 + in order to elucidate thelight-in- duced relaxation pathways populated upon excitation in the longer wavelength range of its absorption spectrum. The computational resultsshow that after the initial excitation, metal (Ru) to ligand (tpphz)chargetransfer (MLCT) triplet states are energeticallyaccessible, but that an ET towardthe catalytic center(PdCl 2 )from thesestates is aslow process, with estimated time constantsabove 1ns. Instead, the cal- culations predict that low-lying Pd-centered states are effi- ciently populated—assoc iated to an energy transfer toward the catalytic center.Thus,itispostulated that thesestates lead to the dissociation of aCl @ and are consequently re- sponsible for the experimentally observed degradation of the catalytic center.Following dissociation, it is shown that the ET rates from the MLCT states to the charge separated statesare significantly increased (i.e. 10 4 –10 6 timeslarger). This demonstrates that alteration of the catalytic center gen- eratesefficientchargeseparation.

Authors

• Magdalena Staniszewska link open in new tab ,
• Stephan Kupfer,
• prof. dr hab. Julien Guthmuller link open in new tab