Phonon-Mediated Ultrafast Hole Transfer from Photoexcited CdSe Quantum Dots to Black Dye
Published in Computational Photocatalysis Modeling of Photophysics and Photochemistry at Interfaces, 2019
We have applied non-adiabatic molecular dynamics (NAMD) and the Fewest Switching Surface Hopping (FSSH) method to simulate the energy dissipation and charge transfer processes in a CdSe quantum dot (QD) functionalized by the tris-thiocyanato-ruthenium (II) terpyridine complex, referred to as black dye. Our calculations reveal ultrafast hole transfer from the photoexcited QD to the dye, despite a significant energy splitting between QD’s and dye’s occupied states. The mechanism of such ultrafast QD-to-dye hole transfer is rationalized by strong non-adiabatic couplings between the delocalized surface orbitals of the QD and the high-frequency vibrations of isothiocyanate ligands of the black dye. This mechanism is also confirmed by a very rapid loss of coherency of the excitation due to strong electronic couplings with vibrational modes of the dye.
Recommended citation: Cui, Peng;Jabed, Mohammed;Vogel, Dayton J.;Kilina, Svetlana . Computational Photocatalysis: Modeling of Photophysics and Photochemistry at Interfaces 2019, 1331(),137-156-. DOI:doi:10.1021/bk-2019-1331.ch006.
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