Szalewicz Krzysztof, Jeziorski Bogumił
Department of Physics and Astronomy, University of Delaware, Newark, DE, 19716, USA.
Faculty of Chemistry, University of Warsaw, Pasteura 1, 02093, Warsaw, Poland.
J Mol Model. 2022 Aug 25;28(9):273. doi: 10.1007/s00894-022-05190-z.
Symmetry-adapted perturbation theory (SAPT) is a method for computational studies of noncovalent interactions between molecules. This method will be discussed here from the perspective of establishing the paradigm for understanding mechanisms of intermolecular interactions. SAPT interaction energies are obtained as sums of several contributions. Each contribution possesses a clear physical interpretation as it results from some specific physical process. It also exhibits a specific dependence on the intermolecular separation R. The four major contributions are the electrostatic, induction, dispersion, and exchange energies, each due to a different mechanism, valid at any R. In addition, at large R, SAPT interaction energies are seamlessly connected with the corresponding terms in the asymptotic multipole expansion of interaction energy in inverse powers of R. Since such expansion explicitly depends on monomers' multipole moments and polarizabilities, this connection provides additional insights by rigorously relating interaction energies to monomers' properties.
对称适配微扰理论（SAPT）是一种用于分子间非共价相互作用计算研究的方法。本文将从建立理解分子间相互作用机制的范式这一角度来讨论该方法。SAPT相互作用能是通过几种贡献的总和得到的。每种贡献都有明确的物理解释，因为它源于某些特定的物理过程。它还表现出对分子间距离R的特定依赖性。四个主要贡献是静电能、诱导能、色散能和交换能，每个都源于不同的机制，在任何R值下都有效。此外，在大R时，SAPT相互作用能与相互作用能以R的负幂次表示的渐近多极展开中的相应项无缝连接。由于这种展开明确依赖于单体的多极矩和极化率，这种联系通过将相互作用能与单体性质严格关联起来提供了额外的见解。
