Range Separation of the Interaction Potential in Intermolecular and Intramolecular Symmetry-Adapted Perturbation Theory,Journal of Chemical Theory and Computation

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Range Separation of the Interaction Potential in Intermolecular and Intramolecular Symmetry-Adapted Perturbation Theory
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2024-09-10 , DOI: 10.1021/acs.jctc.4c00608
Du Luu ₁ , Clemence Corminboeuf ₂ , Konrad Patkowski ₁

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Symmetry-adapted perturbation theory (SAPT) is a popular and versatile tool to compute and decompose noncovalent interaction energies between molecules. The intramolecular SAPT (ISAPT) variant provides a similar energy decomposition between two nonbonded fragments of the same molecule, covalently connected by a third fragment. In this work, we explore an alternative approach where the noncovalent interaction is singled out by a range separation of the Coulomb potential. We investigate two common splittings of the 1/r potential into long-range and short-range parts based on the Gaussian and error functions, and approximate either the entire intermolecular/interfragment interaction or only its attractive terms by the long-range contribution. These range separation schemes are tested for a number of intermolecular and intramolecular complexes. We find that the energy corrections from range-separated SAPT or ISAPT are in reasonable agreement with complete SAPT/ISAPT data. This result should be contrasted with the inability of the long-range multipole expansion to describe crucial short-range charge penetration and exchange effects; it shows that the long-range interaction potential does not just recover the asymptotic interaction energy but also provides a useful account of short-range terms. The best consistency is attained for the error-function separation applied to all interaction terms, both attractive and repulsive. This study is the first step toward a fragmentation-free decomposition of intramolecular nonbonded energy.

中文翻译：

分子间和分子内对称性微扰理论中相互作用势的范围分离

对称适应微扰理论 (SAPT) 是一种流行的多功能工具，用于计算和分解分子之间的非共价相互作用能。分子内 SAPT (ISAPT) 变体在同一分子的两个非键合片段之间提供类似的能量分解，并通过第三个片段共价连接。在这项工作中，我们探索了一种替代方法，其中通过库仑势的范围分离来挑选出非共价相互作用。我们基于高斯函数和误差函数研究了 1/r 势向长程和短程部分的两种常见分裂，并通过长程贡献近似整个分子间/片段间相互作用或仅其有吸引力的项。这些范围分离方案针对许多分子间和分子内复合物进行了测试。我们发现范围分离 SAPT 或 ISAPT 的能量修正与完整的 SAPT/ISAPT 数据相当一致。这一结果应与无法描述关键的短程电荷穿透和交换效应的长程多极展开形成对比；它表明长程相互作用势不仅恢复了渐近相互作用能，而且还提供了短程项的有用解释。将误差函数分离应用于所有相互作用项（无论是吸引项还是排斥项）都可以获得最佳一致性。这项研究是实现分子内非键能无碎片分解的第一步。

更新日期：2024-09-10

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