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12.14 The XPol+SAPT (XSAPT) Method

12.14.1 Introduction

(February 4, 2022)

The “XSAPT” method, which may be regarded either as an acronym for “XPol+SAPT” or for “extended” symmetry adapted perturbation theory (SAPT), was originally introduced by Jacobson and Herbert511, 456 as a low-scaling, systematically-improvable method for intermolecular interactions that could be applicable to large systems. The idea was to replace the need for empirical parameters in the XPol method with on-the-fly evaluation of exchange-repulsion and dispersion interactions via pairwise-additive SAPT. Stated differently, XSAPT uses XPol to evaluate many-body (non-pairwise-additive) polarization effects, but then assumes that dispersion and exchange-repulsion interactions are pairwise additive, and evaluates them via pairwise SAPT0 or SAPT0(KS) calculations. The method was significantly extended by Lao, Herbert, and co-workers,630, 631, 633, 635, 636, 162, 705, 390 with various approximations applied in place of the SAPT0 or SAPT0(KS) dispersion terms,161 which are both the least accurate and most expensive contributions to second-order SAPT. Overviews of of XSAPT-based methods can be found in Refs. 633 and 161 and implementation details can be found in Refs. 456, 635, and 705. In particular, the XSAPT+MBD method162 stands out as a way to obtain qualitative insight about noncovalent interactions in large systems, backed by quantitative energetics calculations.161 In many cases, this type of analysis has upended textbook “conventional wisdom", as reviewed in Ref. 462.