Overcoming Artificial Multipoles in Intramolecular Symmetry-Adapted Perturbation Theory.

Intramolecular symmetry-adapted perturbation theory (ISAPT) is a method to compute and decompose the noncovalent interaction energy between two molecular fragments A and B covalently connected via a linker C . However, the existing ISAPT algorithm displays several issues for many fragmentation patterns (that is, specific assignments of atoms to the A / B / C subsystems), including an artificially repulsive electrostatic energy (even when the fragments are hydrogen-bonded) and very large and mutually cancelling induction and exchange-induction terms. We attribute those issues to the presence of artificial dipole moments at the interfragment boundary, as the atoms of A and B directly connected to C are missing electrons on one of their hybrid orbitals. Therefore, we propose several new partitioning algorithms which reassign one electron, on a singly occupied link hybrid orbital, from C to each of A / B . Once the contributions from these link orbitals are added to fragment density matrices, the computation of ISAPT electrostatic, induction, and dispersion energies proceeds exactly as normal, and the exchange energy expressions need only minor modifications. Among the link partitioning algorithms introduced, the so-called ISAPT(SIAO1) approach (in which the link orbital is obtained by a projection onto the intrinsic atomic orbitals (IAOs) of a given fragment followed by orthogonalization to this fragment's occupied space) leads to reasonable values of all ISAPT corrections for all fragmentation patterns, and exhibits a fast and systematic basis set convergence. This improvement is made possible by a significant reduction in magnitude (even though not a complete elimination) of the unphysical dipole moments at the interfragment boundaries. We demonstrate the utility of the improved ISAPT partitioning by examining intramolecular interactions in several pentanediol isomers, examples of linear and branched alkanes, and the open and closed conformations of a family of N-arylimide molecular torsion balances.