Basis Set Superposition Errors in the Many-Body Expansion of Molecular Properties
Basis Set Superposition Errors in the Many-Body Expansion of Molecular Properties
复制标题
分子性质多体展开中的基组叠加误差
DOI：
10.1021/acs.jpca.9b03864
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发表时间：
2019
影响因子：
--
通讯作者：
Peyton, Benjamin G.
Crawford
中科院分区：
文献类型：
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作者：
Peyton, Benjamin G.
Crawford
研究了高阶响应特性的受尊敬的多体展开（MBE）收敛性差的根本原因，特别关注基组叠加误差的影响。相互作用能，偶极矩，动态极化率，和特定的旋转计算三个手性溶质在明确的水笼大小不同，使用分子束外延，包括基于网站的网站功能平衡（或“全集群”的基础上）的方法校正。此外，我们认为其他可能的原因所观察到的分子束外延的振荡行为，包括数值精度，基组大小，密度泛函的选择，和快照的几何形状。我们的研究结果表明，平衡校正是必要的阻尼振荡，实现合理的收敛的MBE高阶性能。然而，由于其固有的非加性性质，膨胀中的振荡不能完全消除手性性质，如比旋光度，从而限制了MBE用于研究溶剂化手性化合物的功效。
The underlying reasons for the poor convergence of the venerated many-body expansion (MBE) for higher-order response properties are investigated, with a particular focus on the impact of basis set superposition errors. Interaction energies, dipole moments, dynamic polarizabilities, and specific rotations are computed for three chiral solutes in explicit water cages of varying sizes using the MBE including corrections based on the site–site function counterpoise (or “full-cluster” basis) approach. In addition, we consider other possible causes for the observed oscillatory behavior of the MBE, including numerical precision, basis set size, choice of density functional, and snapshot geometry. Our results indicate that counterpoise corrections are necessary for damping oscillations and achieving reasonable convergence of the MBE for higher order properties. However, oscillations in the expansion cannot be completely eliminated for chiroptical properties such as specific rotations due to their inherently nonadditive nature, thus limiting the efficacy of the MBE for studying solvated chiral compounds.