Three new data sets for intermolecular interactions, AHB21 for anion-neutral dimers, CHB6 for cation-neutral dimers, and IL16 for ion pairs, are assembled here, with complete-basis CCSD(T) results for each. These benchmarks are then used to evaluate the accuracy of the single-exchange approximation that is used for exchange energies in symmetry-adapted perturbation theory (SAPT), and the accuracy of SAPT based on wave function and density-functional descriptions of the monomers is evaluated. High-level SAPT calculations afford poor results for these data sets, and this includes the recently proposed "gold", "silver", and "bronze standards" of SAPT, namely, SAPT2+(3)-δMP2/aug-cc-pVTZ, SAPT2+/aug-cc-pVDZ, and sSAPT0/jun-cc-pVDZ, respectively [ Parker , T. M. , et al. , J. Chem. Phys. 2014 , 140 , 094106 ]. Especially poor results are obtained for symmetric shared-proton systems of the form X(-)···H(+)···X(-), for X = F, Cl, or OH. For the anionic data set, the SAPT2+(CCD)-δMP2/aug-cc-pVTZ method exhibits the best performance, with a mean absolute error (MAE) of 0.3 kcal/mol and a maximum error of 0.7 kcal/mol. For the cationic data set, the highest-level SAPT method, SAPT2+3-δMP2/aug-cc-pVQZ, outperforms the rest of the SAPT methods, with a MAE of 0.2 kcal/mol and a maximum error of 0.4 kcal/mol. For the ion-pair data set, the SAPT2+3-δMP2/aug-cc-pVTZ performs the best among all SAPT methods with a MAE of 0.3 kcal/mol and a maximum error of 0.9 kcal/mol. Overall, SAPT2+3-δMP2/aug-cc-pVTZ affords a small and balanced MAE (<0.5 kcal/mol) for all three data sets, with an overall MAE of 0.4 kcal/mol. Despite the breakdown of perturbation theory for ionic systems at short-range, SAPT can still be saved given two corrections: a "δHF" correction, which requires a supermolecular Hartree-Fock calculation to incorporate polarization effects beyond second order, and a "δMP2" correction, which requires a supermolecular MP2 calculation to account for higher-order induction-dispersion coupling. These corrections serve to remove artifacts introduced by the single exchange approximation in the exchange-induction and exchange-dispersion interactions, and obviate the need for ad hoc scaling of the first- and second-order exchange energies. Finally, some density-functional and MP2-based electronic structure methods are assessed as well, and we find that the best density-functional method for computing binding energies in these data sets is B97M-V/aug-cc-pVTZ, which affords a MAE of 0.4 kcal/mol, whereas complete-basis MP2 affords an MAE of 0.3 kcal/mol.

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An approach to evaluate the second-order exchange-induction energies of symmetry-adapted intermolecular perturbation theory (SAPT) for single-determinant ground-state monomer wavefunctions has been derived. This approach is correct to all orders of the intermonomer overlap, that is, it takes multiple electron exchange between the monomers into account. The resulting formulae can be written in a compact way and implemented efficiently. Here, the method is employed to investigate the performance of the S 2 -or single-exchange approximation at the Hartree-Fock-SAPT level. The list of test systems comprises the prototypical van der Waals-and hydrogen-bridge complexes Ne 2 , Ar-HF, and (H 2 O) 2 , but also the systems HeCl -, NeNa ? and Li ? F -involving closed-shell ions. It was found that the errors introduced by the S 2 -approximation are more pronounced for the secondorder exchange-induction energy than for the first-order exchange energy. While these errors tend to be negligible throughout the well region of complexes such as the neon dimer, they start to be significant in the repulsive part of the well regions of systems such as the water dimer, and in particular for the ionic lithium fluoride molecule. The consequences of these findings for the Hartree-Fock level estimate of higher-order induction plus exchange-induction energies, which is frequently employed in SAPT are also discussed.

We propose a physically motivated decomposition of density functional theory (DFT) 3-body nonadditive interaction energies into the exchange and density-deformation (polarization) components. The exchange component represents the effect of the Pauli exclusion in the wave function of the trimer and is found to be challenging for density functional approximations (DFAs). The remaining density-deformation nonadditivity is less dependent upon the DFAs. Numerical demonstration is carried out for rare gas atom trimers, Ar-HX (X = F, Cl) complexes, and small hydrogen-bonded and van der Waals molecular systems. None of the tested semilocal, hybrid, and range-separated DFAs properly accounts for the nonadditive exchange in dispersion-bonded trimers. By contrast, for hydrogen-bonded systems, range-separated DFAs achieve a qualitative agreement to within 20% of the reference exchange energy. A reliable performance for all systems is obtained only when the monomers interact through the Hartree-Fock potential in the dispersion-free Pauli blockade scheme. Additionally, we identify the nonadditive second-order exchange-dispersion energy as an important but overlooked contribution in force-field-like dispersion corrections. Our results suggest that range-separated functionals do not include this component, although semilocal and global hybrid DFAs appear to imitate it in the short range.

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