Fragment Exchange Potential for Realizing Pauli Deformation of Interfragment Interactions

Chen, X.; Gao, J.. Journal of Physical Chemistry Letters, 2020, 11, 4008−4016.

In fragment-based methods, the lack of explicit short-range exchange interactions between monomers can result in unphysical deformation in charge density. In this study, we describe a fragment exchange potential (XFP) to explicitly account for interfragmental Pauli deformation. In our implementation, a Kohn–Sham exchange potential is adopted along with the Yukawa potential. The method has been validated by comparison of the computed exchange energies using the XFP potential with results obtained from antisymmetrized fragmental orbitals on the S66×8 data set containing 528 bimolecular interactions of equilibrium and arbitrary geometries. It was also found that it is only necessary to deploy numerical grids on atoms within their van der Waals contacts, significantly reducing the small, albeit extra, computational cost. We anticipate that the XFP presented here may be applied to molecular dynamics simulations of macromolecules using a fragment-based quantum mechanical potential with improved SCF convergence and computational accuracy.