Range separation of the interaction potential in intermolecular and intramolecular symmetry-adapted perturbation theory

TL;DR

This paper introduces a range separation approach in symmetry-adapted perturbation theory (SAPT) to better decompose noncovalent interactions, showing that long-range potential corrections can effectively approximate full interaction energies.

Contribution

It proposes a novel range separation method for SAPT and ISAPT, improving the accuracy of energy decomposition without fragmentation.

Findings

Range-separated SAPT approximates full SAPT energies well.

Error-function separation yields the best consistency for all interaction terms.

Long-range potential captures both asymptotic and short-range effects effectively.

Abstract

Symmetry-adapted perturbation theory (SAPT) is a popular and versatile tool to compute and decompose noncovalent interaction energies between molecules. The intramolecular SAPT (ISAPT) variant provides a similar energy decomposition between two nonbonded fragments of the same molecule, covalently connected by a third fragment. In this work, we explore an alternative approach where the noncovalent interaction is singled out by a range separation of the Coulomb potential. We investigate two common splittings of the $1/r$ potential into long-range and short-range parts based on the Gaussian and error functions, and approximate either the entire intermolecular/interfragment interaction or only its attractive terms by the long-range contribution. These range separation schemes are tested for a number of intermolecular and intramolecular complexes. We find that the energy corrections from range-separated SAPT or ISAPT are in reasonable agreement with complete SAPT/ISAPT data. This result should be contrasted with the inability of the long-range multipole expansion to describe crucial short-range charge penetration and exchange effects; it shows that the long-range interaction potential does not just recover the asymptotic interaction energy but also provides a useful account of short-range terms. The best consistency is attained for the error-function separation applied to all interaction terms, both attractive and repulsive. This study is the first step towards a fragmentation-free decomposition of intramolecular nonbonded energy.