Hole Polarons in Cadmium Chalcogenides as an Interfacial Phenomenon

Quantum nanorods are attractive materials for photocatalytic reduction and oxidation reactions because of their tunable morphology and bandgaps. Holes prepared in these materials readily trap to the surface, where they form polarons that diffuse over timescales from nanoseconds to microseconds. Modeling these dynamics is a fundamental challenge because potential energy functions are parameterized to reproduce properties on the ground electronic state. By using a linear response theory, we extend empirical potentials to simulate long-lived excited states. With these methods, we study polaron motion in the presence of ligands and solvent at the nanoparticle interface. I will show how hole mobility depends on interfacial fluctuations. Using those data, I will suggest experimental surface and solvent treatments to improve hole diffusion rates to overcome a kinetic bottleneck in photoredox chemistry using these materials.