CHAPTER 1. Modern Computational Approaches to Understanding Interactions of Aromatics
Michael Lewis, Christina Bagwill, Laura K. E. Hardebeck, Selina Wireduaah · Monographs in supramolecular chemistry · 2016
This chapter briefly describes how early computational work aimed at understanding, and describing, arene–arene and cation–arene interactions focused on the aromatic quadrupole moment, and fairly soon thereafter Hammett substituent constants. Modern computational approaches to understanding these interactions still invoke Hammett substituent constants, however, multi-parameter equations with a variety of substituent constants are now commonly employed to understand and predict the strength of arene–arene and cation–arene binding. In addition, energy decomposition methods have become a common computational tool in understanding non-covalent interactions of aromatics. Furthermore, there is growing computational evidence that through-space substituent–substituent interactions are important in understanding arene–arene interactions, and analogous cation–substituent interactions are important in understanding cation–arene interactions. The details of these modern areas of computational research are presented.