Levels of symmetry adapted perturbation theory (SAPT). II. Convergence of interaction energy components

27 April 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Symmetry adapted perturbation theory (SAPT) is a valuable theoretical technique use- ful in quantifying intermolecular interaction energies in terms of four physically meaningful components: electrostatics, exchange-repulsion, induction, and London dispersion. We present a systematic analysis of the convergence of SAPT total and component energies with respect to level of theory and basis set using an extended database of 4567 dimer geometries. Our analysis supports the use of SAPT0/aug-cc-pVDZ over previously recommended sSAPT0/jun-cc-pVDZ as an economical level of SAPT. Our previous recommendations of SAPT2+/aug-cc-pVDZ and SAPT2+(3)δMP2/aug-cc-pVTZ as medium and high cost variants, respectively, remain unchanged. However, SAPT0/aug-cc-pVDZ and SAPT2+/aug-cc-pVDZ total interaction energies on average rely on error cancellations, so their use in parameterizing SAPT-based force fields and intermolecular potentials should be used with caution. SAPT2+(3)δMP2/aug-cc-pVTZ does show quantitatively accurate component energies, making it the preferred choice for all applications when feasible. Lastly, we introduce a focal point technique which approaches the accuracy of SAPT2+(3)δMP2/aug-cc-pVTZ with a significantly reduced cost.


non-covalent interactions
interaction energies
symmetry-adapted perturbation theory
London dispersion forces


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