Ab initio calculations of through-space and through-bond charge-transfer properties of interacting Janus-like PbSe and CdSe quantum dot heterostructures

Heterostructure quantum dots (QDs) are composed of two QD nanocrystals (NCs) conjoined at an interface. They are useful in applications such as photovoltaic solar cells. The properties of the interface between the NCs determine the efficiency of electron–hole recombination rates and charge transfer. Therefore, a fundamental understanding of how this interface works between the two materials is useful. To contribute to this understanding, we simulated two isolated heterostructure QD models with Janus-like geometry composed of Cd33Se33 + Pb68Se68 NCs. The first Janus-like model has a bond connection between the two NCs and is approximately 16 × 17 × 29 Å3 in size. The second model has a through-space connection between the NCs and is approximately 16 × 17 × 31 Å3. We use density functional theory to simulate the ground state properties of these models. Nonadiabatic on-the-fly couplings calculations were then used to construct the Redfield Tensor, which described the excited state dynamics due to nonradiative relaxation. From our results, we identified a qualitative trend which shows that having a bond connecting the two NCs reduces hole relaxation time. We also identified for a sample of electron–hole excitations pairs that the through-bond model allows for a net positive or negative numerical net charge transfer, depending on the excitation pair.