First-Principles Modeling of Non-Covalent Interactions in Supramolecular Systems: The Role of Many-Body Effects

Supramolecular host-guest systems play an important role for a wide range of applications in chemistry and biology. The prediction of the stability of host-guest complexes represents a great challenge to first-principles calculations due to an interplay of a wide variety of covalent and noncovalent interactions in these systems. In particular, van der Waals (vdW) dispersion interactions frequently play a prominent role in determining the structure, stability, and function of supramolecular systems. On the basis of the widely used benchmark case of the buckyball catcher complex (C60@C60H28), we assess the feasibility of computing the binding energy of supramolecular host-guest complexes from first principles. Large-scale diffusion Monte Carlo (DMC) calculations are carried out to accurately determine the binding energy for the C60@C60H28 complex (26 ± 2 kcal/mol). On the basis of the DMC reference, we assess the accuracy of widely used and efficient density-functional theory (DFT) methods with dispersion interactions. The inclusion of vdW dispersion interactions in DFT leads to a large stabilization of the C60@C60H28 complex. However, DFT methods including pairwise vdW interactions overestimate the stability of this complex by 9-17 kcal/mol compared to the DMC reference and the extrapolated experimental data. A significant part of this overestimation (9 kcal/mol) stems from the lack of dynamical dielectric screening effects in the description of the molecular polarizability in pairwise dispersion energy approaches. The remaining overstabilization arises from the isotropic treatment of atomic polarizability tensors and the lack of many-body dispersion interactions. A further assessment of a different supramolecular system - glycine anhydride interacting with an amide macrocycle - demonstrates that both the dynamical screening and the many-body dispersion energy are complex contributions that are very sensitive to the underlying molecular geometry and type of bonding. We discuss the required improvements in theoretical methods for achieving "chemical accuracy" in the first-principles modeling of supramolecular systems.