Through our analyses of tractable model systems and benchmark molecular systems, we find that Vendi sampling indeed excels in cases that are defined by high free energy barriers in two ways: it rapidly covers the local minima of the free energy landscape and enables fast mixing across free energy barriers to allow for fast convergence of free energy estimates. Future work will explore whether Vendi sampling can benefit from more advanced kernel functions, e.g. in the context of sampling interfacial water molecules, which may be important for molecular processes such as ligand binding. Exploring alternative annealing strategies of the Vendi force during sampling may lead to further efficiency gains.