Semiconductor Quantum Dots in the Cluster Regime

The exciton Bohr radius is a defining feature in conventional quantum dot physics. Three distinct confinement regimes are usually recognized: the weak, intermediate, and strong confinement regimes. Which of these is relevant depends on the relative size of the quantum dot in terms of the exciton Bohr radius. However, this classification is primarily based on the linear optical properties of the nanocrystal. During the transition from the molecule to the bulk crystal, structural, mechanical, thermal, and chemical properties change as well. In this review, we discuss the cluster regime, where the exciton experiences extreme confinement. In the cluster regime, not only do linear optical properties deviate significantly from the effective mass approximation, but other material properties also begin to deviate from their bulk values. These deviations are only observable in the size regime, where the intrinsic length scales are much smaller than the exciton Bohr radius. Crucially, computational methods allow chemists to explore this region far more quantitatively than in the past.