This article describes density-functional-theory- (DFT-) based calculations of the rate constants for radiative (kR) and nonradiative (kNR) decay from the lowest singlet excited state (S1) to the ground state (S0) of a Cd16Se13 cluster ligated with various molecules in various binding geometries. The value of kR is suppressed by ligands whose localized orbitals, as a result of their binding geometry, become the cluster's frontier orbitals and, thereby, decrease the overlap of the electron densities of the HOMO and LUMO necessary for efficient dipole coupling. Thiolate ligands in a monodentate geometry and dithioate ligands in a bridging geometry decrease kR in this manner. The value of kNR is also sensitive to the binding geometries of the ligands: binding geometries that are less rigid yield a greater change in nuclear coordinates between the S1 and S0 electronic states, which, in turn, increases the rate of nonradiative decay by maximizing the vibronic coupling between the band-edge exciton and the vibrational modes of the ligands. This work suggests that the photoluminescence quantum yield of CdSe nanoparticles can be maximized by ensuring that the bridging binding mode is the dominant binding mode of the ligands; bridging modes decrease the nonradiative decay rate and eliminate mid-band-gap trap states in all cases studied, except for dithioate ligands. (Chemical Equation Presented).
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Electronic, Optical and Magnetic Materials
- Surfaces, Coatings and Films