As expected based on Section 4.1.2, the same number of windows were normally selected between the bound and free legs, and the number of windows approximately halved when the thermodynamic speed was doubled (Figure ). A speed of 2.0 kcal mol -1 appeared close to the maximum, because low off-diagonal overlaps were observed (according to the rule-of-thumb that off-diagonal values should not be lower than 0.03). This is in agreement with the results of Rizzi. 64 No.windows ) and b) overlap matrices using a manually-optimised λ schedule, and using the automated method to space windows with thermodynamic speeds of 0.5, 1.0, 2.0, and 4.0 kcal mol -1 . The automated method produces more consistent off-diagonal overlap than the manually-optimised schedule. Plots for all other stages are shown in Section S10