Double hybrids with higher proportions of Fock exchange and/or range separation exhibit increased D e and decreased r e , thereby reducing underbinding errors for the pyrene excimer. This demonstrates that their improved description of CT is crucial for pyrene excimer binding, despite its relatively smaller role (compared to benzene excimer binding). Methods that tend to overbind the benzene excimer, predicting excessively short r e (even if D e is not overestimated), have a reduced tendency to do the same for the pyrene excimer. Here, spinscaled functionals are far less likely to exhibit this incorrect well-position, possibly due to a better balance between shortand long-range correlation effects.