Surface defects and organic surface-capping
ligands affect the
photoluminescence properties of semiconductor quantum dots (QDs) by
altering the rates of competing nonradiative relaxation processes.
In this study, broadband two-dimensional electronic spectroscopy reveals
that absorption of light by QDs prepares vibronic excitons, excited
states derived from quantum coherent mixing of the core electronic
and ligand vibrational states. Rapidly damped coherent wavepacket
motions of the ligands are observed during hot-carrier cooling, with
vibronic coherence transferred to the photoluminescent state. These
findings suggest a many-electron, molecular theory for the electronic
structure of QDs, which is supported by calculations of the structures
of conical intersections between the exciton potential surfaces of
a small ammonia-passivated model CdSe nanoparticle.