Ligand Induced Spectral Changes in CdSe Quantum Dots.

The rational design of ligand molecules has earned lots of attention as an elegant means to tailor the electronic and optical properties of semiconductor quantum dots (QDs). Aromatic dithiocarbamate molecules, in particular, are known to greatly influence the optoelectronic properties of CdSe QDs, red-shifting the absorption features and enhancing the photoluminescence. Here, we present an integrated computational study, which combines ab initio molecular dynamics and excited state calculations including thousands of excitations, aimed at understanding the impact of this kind of surface ligand on the optoelectronic properties of CdSe QDs. We demonstrate that the valence electronic states of the dithiocarbamate molecules, mostly localized in the anchoring moiety, are responsible for the red-shift of the absorption features of capped CdSe QDs. Ligands develop interfacial electronic states close to the band edges of the CdSe, which enhance the absorption features of the QD and might open new channels for the radiative decay from the excited state, improving optical emission. Hybridized QD/ligand states could also funnel interfacial charge transfer between the inorganic core and surface molecules, a process that lies at the heart of many photovoltaic and photocatalytic devices. This work may pave the way toward the design of new capping ligands that, adsorbed on the QD surface, could provide control over the optoelectronic properties of the semiconductor core.