Ultrafast fs coherent excitonic dynamics in CdSe quantum dots assemblies addressed and probed by 2D electronic spectroscopy

We show in a joint experimental and theoretical study that ultrafast femto-second (fs) electronic coherences can be characterized in semiconducting colloidal quantum dot (QD) assemblies at room temperature. The dynamics of the electronic response of ensembles of CdSe QDs in the solution and of QD dimers in the solid state is probed by a sequence of 3 fs laser pulses as in two-dimensional (2D) electronic spectroscopy. The quantum dynamics is computed using an excitonic model Hamiltonian based on the effective mass approximation. The Hamiltonian includes the Coulomb, spin–orbit, and crystal field interactions that give rise to the fine structure splittings. In the dimers studied, the interdot distance is sufficiently small to allow for an efficient interdot coupling and delocalization of the excitons over the two QDs of the dimer. To account for the inherent few percent size dispersion of colloidal QDs, the optical response is modeled by averaging over
an ensemble of 2000 dimers. The size dispersion is responsible for an inhomogeneous broadening that limits the lifetimes of the excitonic coherences that can be probed to about 150 fs–200 fs. Simulations and experimental measurements in the solid state and in the solution demonstrate that during that time scale, a very rich electronic coherent dynamics takes place that involves several types of intradot and interdot (in the case of dimers) coherences. These electronic coherences exhibit a wide range of beating periods and provide a versatile basis for a quantum information processing device on a fs time scale at room temperature.