Rationalizing Aggregate Structures with Orbital Contributions to the Exchange-Repulsion Energy.

It is shown that repulsive interactions have a crucial influence on the structure of prototypical non-covalently bonded systems. To explain this, we propose a molecular orbital-based model for the exchange-repulsion contribution to the total interaction energy. As a central result, our model shows that energetically preferred aggregate structures frequently exhibit reduced exchange repulsion, which can be deduced from the nodal structure of certain occupied orbitals. This is used to explain key features of the intermolecular potentials of the Cl 2 -He, benzene-benzene, and benzene-hexafluorobenzene aggregates, which are not correctly reproduced by commonly applied electrostatic models.