It is the t_C2/t_C1 ratio in Scheme 2 rather than the transition probabilities that determine the paradoxical shifts in the linkage between components and states. (A–C) Plots of τ_E1 and τ_E2 against k_(C2-C1) in Scheme 2 as k_(C2-C1) is changed over six orders of magnitude. These changes in k_(C2-C1) change t_C2 from 1 s to 1 μs as t_C1 remains constant at 1 ms. The resulting change in the t_C2/t_C1 ratio is plotted at the bottom of the figure. Plots are presented for three different transition probabilities ratios for P_C1-C2/P_C1-O1 of 0.999/0.001 (A), 0.5/0.5 (B), and 0.001/0.999 (C). For all three transition probability ratios, τ_E1 tracks t_C1 and τ_E2 tracks t_C2 (with an offset in A and B) when t_C2 >> t_C1 and then τ_E1 tracks t_C2 and τ_E2 tracks t_C1 (with an offset in A and B) when t_C2 << t_C1. The inset in C shows the switch in tracking follows the same pattern as in A and B. (D–F) Areas of E₁, E₂, {C₁}, and {C₁C₂} as a function of k_C1-C2 and the resulting t_C2/t_C1 ratio. In D, a log scale is used so that the change in the small area of E₁ can be seen. The corresponding change in the area of E₂ is too small compared with the large area of E₂ to be seen. Note that the paradoxical shifts in time constants and areas of the exponential components as a function of the t_C2/t_C1 ratio are still observed for a 10⁶-fold change in transition probabilities.