To generate the initial geometries for Rh single-atom sampling, we utilized the GOCIA code . GOCIA applies the BLDA (see computational details), which constrains the distances between each atom and its first and second nearest neighbors to follow a normal distribution. This method produces chemically relevant initial structures that are easier to converge in simulations. For each TiO2 support, 20 distinct initial structures were generated for Rh single-atom sampling. The identified global minimum configurations are shown in Figure .