论文标题

克服分子内对称性扰动理论中的人造多物

Overcoming Artificial Multipoles in Intramolecular Symmetry-Adapted Perturbation Theory

论文作者

Luu, Du, Patkowski, Konrad

论文摘要

分子内对称性适应的扰动理论(ISAPT)是一种计算和分解两个分子片段A和B之间的非共价相互作用能量。术语。我们将这些问题归因于剥离边界处的人造偶极矩,因为直接连接到C的A和B的原子在其一个混合轨道上缺少电子。因此,我们提出了几种新的分区算法,这些算法将一个电子(从C到A/b的每一个)重新分配一个电子,即单独占据的链接混合轨道。一旦将这些链路轨道的贡献添加到片段密度矩阵中,ISAPT静电,诱导和色散能的计算将完全正常进行,而Exchange Enferage Enspressions仅需要较小的修改。在引入的链路分区算法中,ISAPT(SIAO1)方法(其中通过投影对给定片段的固有原子轨道进行投影获得链路轨道,然后对该片段的占用空间进行正交化),导致所有片段校正的合理价值,以均衡范围校正片段和系统的互惠互整合。通过大小(即使不是完全消除)在腐蚀边界处的非物理偶极矩的大幅度降低(即使不是完全消除)可以改善这种改善。我们通过检查了几种五二二醇异构体的分子内相互作用,线性和分支烷烃的示例,以及一个N-雅利林分子扭转平衡的家族的开放和封闭构象,证明了改进的ISAPT分配的实用性。

Intramolecular symmetry-adapted perturbation theory (ISAPT) is a method to compute and decompose the noncovalent interaction energy between two molecular fragments A and B connected via a linker C. The existing ISAPT algorithm displays several issues for many fragmentation patterns, including an artificially repulsive electrostatic energy (even when the fragments are hydrogen-bonded) and very large and mutually cancelling induction and exchange-induction terms. We attribute those issues to the artificial dipole moments at the interfragment boundary, as the atoms of A and B directly connected to C are missing electrons on one of their hybrid orbitals. Therefore, we propose several new partitioning algorithms which reassign one electron, on a singly occupied link hybrid orbital, from C to each of A/B. Once the contributions from these link orbitals are added to fragment density matrices, the computation of ISAPT electrostatic, induction, and dispersion energies proceeds exactly as normal, and the exchange energy expressions need only minor modifications. Among the link partitioning algorithms introduced, the ISAPT(SIAO1) approach (in which the link orbital is obtained by a projection onto the intrinsic atomic orbitals of a given fragment followed by orthogonalization to this fragment's occupied space) leads to reasonable values of all ISAPT corrections for all fragmentation patterns and exhibits fast and systematic basis set convergence. This improvement is made possible by a significant reduction in magnitude (even though not a complete elimination) of the unphysical dipole moments at the interfragment boundaries. We demonstrate the utility of the improved ISAPT partitioning by examining intramolecular interactions in several pentanediol isomers, examples of linear and branched alkanes, and the open and closed conformations of a family of N-arylimide molecular torsion balances.

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