The functional properties of molecular systems are generally determined by the sum of many weak non-covalent interactions, and therefore methods for predicting the relative magnitudes of these interactions is fundamental to understanding the relationship between function and structure in chemistry, biology and materials science. This review focuses on the Surface Site Interaction Point (SSIP) approach which describes molecules as a set of points that capture the properties of all possible non-covalent interactions that the molecule might make with another molecule. The first half of the review focuses on the empirical non-covalent interaction parameters, α and β, and provides simple rules of thumb to estimate free energy changes for interactions between different types of functional group. These parameters have been used to have been used to establish a quantitative understanding of the role of solvent in solution phase equilibria, and to describe non-covalent interactions at the interface between macroscopic surfaces as well as in the solid state. The second half of the review focuses on a computational approach for obtaining SSIPs and applications in multi-component systems where many different interactions compete. Ab initio calculation of the Molecular Electrostatic Potential (MEP) surface is used to derive an SSIP description of a molecule, where each SSIP is assigned a value equivalent to the corresponding empirical parameter, α or β. By considering the free energies of all possible pairing interactions between all SSIPs in a molecular ensemble, it is possible to calculate the speciation of all intermolecular interactions and hence predict thermodynamic properties using the SSIMPLE algorithm. SSIPs have been used to describe both the solution phase and the solid state and provide accurate predictions of partition coefficients, solvent effects on association constants for formation of intermolecular complexes, and the probability of cocrystal formation. SSIPs represent a simple and intuitive tool for describing the relationship between chemical structure and non-covalent interactions with sufficient accuracy to understand and predict the properties of complex molecular ensembles without the need for computationally expensive simulations.

中文翻译：

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非共价相互作用的表面位点相互作用点方法

分子系统的功能特性通常由许多弱的非共价相互作用的总和决定，因此预测这些相互作用的相对大小的方法对于理解化学、生物学和材料科学中功能与结构之间的关系至关重要。本综述侧重于表面位点相互作用点 (SSIP) 方法，该方法将分子描述为一组点，这些点捕获分子可能与另一个分子产生的所有可能的非共价相互作用的特性。综述的前半部分侧重于实证非共价相互作用参数α和β，并提供简单的经验法则来估计不同类型官能团之间相互作用的自由能变化。这些参数已被用于建立对溶剂在溶液相平衡中的作用的定量理解，并描述宏观表面和固态界面之间的非共价相互作用。审查的后半部分侧重于在许多不同交互竞争的多组件系统中获取 SSIP 和应用程序的计算方法。分子静电势 (MEP) 表面的从头计算用于推导分子的 SSIP 描述，其中为每个 SSIP 分配一个等于相应经验参数α或β。通过考虑分子系综中所有 SSIP 之间所有可能配对相互作用的自由能，可以计算所有分子间相互作用的形态，从而使用 SSIMPLE 算法预测热力学性质。SSIP 已被用于描述溶液相和固态，并提供分配系数的准确预测、溶剂对分子间复合物形成的缔合常数的影响以及共晶形成的概率。SSIPs 代表了一种简单直观的工具，用于描述化学结构和非共价相互作用之间的关系，具有足够的准确性来理解和预测复杂分子系综的特性，而无需计算成本高昂的模拟。