Understanding Substituent Effects in Noncovalent Interactions Involving Aromatic Rings

Noncovalent interactions involving aromatic rings such as π-stacking, cation/π, and anion/π interactions are central to many areas of modern chemistry. Decades of experimental studies have provided key insights into the impact of substituents on these interactions, leading to the development of simple intuitive models. However, gas-phase computational studies have raised some doubts about the physical underpinnings of these widespread models. In this Account we review our recent efforts to unravel the origin of substituent effects in π-stacking and ion/π interactions through computational studies of model noncovalent dimers. First, however, we dispel the notion that so-called aromatic interactions depend on…