Two-Dimensional Electronic Spectroscopy Reveals Dynamics within the Bright Fine Structure of CdSe Quantum Dots.

Semiconductor quantum dots are characterized by a discrete excitonic structure featuring coarse as well as fine structure. The lowest fine structure states have splittings into bright-dark states which are now well confirmed by single dot spectroscopy. In contrast, the splitting of the lowest coarse exciton into bright-bright fine structure states has not been observed nor the dynamics between these states. Here, we use the unique combination of time and energy resolution of two-dimensional electronic spectroscopy to directly observe the fine structure splittings into a bright-bright doublet. These splittings are strongly size dependent, with population relaxation on the <100 fs time scale.