The interplay of intra- and intermolecular errors in modeling conformational polymorphs
The interplay of intra- and intermolecular errors in modeling conformational polymorphs
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DOI：
10.1063/5.0088027
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发表时间：
2022-03-14
影响因子：
4.4
通讯作者：
Cruz-Cabeza, Aurora J.
中科院分区：
文献类型：
--
作者：
Beran, Gregory J. O.;Wright, Sarah E.;Cruz-Cabeza, Aurora J.
有机分子晶体的构象多晶型物代表了量子化学的挑战性测试，因为它们需要仔细平衡分子内和分子间的相互作用。本研究探讨了54个分子构象从20组的构象多晶型，沿着的相对晶格能和173二聚体相互作用从6个多晶型集。这些系统进行了研究与各种货车德瓦尔斯包容的密度泛函理论模型;色散校正的自旋分量标度的二阶MOller-Plesset微扰理论（SCS-MP 2D）;和域本地对自然轨道耦合集群单，双，和微扰三元组[DLPNO-CCSD（T）]。我们研究如何在传统的密度泛函离域误差影响单体的构象能，在分子间相互作用的系统误差，以及在整个晶体中发生的错误取消的性质。密度泛函B86 bPBE-XDM、PBE-D4、PBE-MBD、PBE 0-D4和PBE 0-MBD相对于DLPNO-CCSD（T）基准表现出相当大的单体和二体误差，并且预测相对多晶型能量的成功程度在很大程度上依赖于不同类型的分子间相互作用之间或分子内和分子间相互作用之间的误差消除。SCS-MP 2D和欧米茄B 97 M-V型号（在较小程度上）的误差较小，对误差消除的依赖程度较低。柔性化合物的晶体结构预测的影响进行了讨论。最后，从这些构象多晶型物中提取的单体和两体DLPNO-CCSD（T）能量建立了CP 1b和CP 2b基准数据集，这些数据集可用于在具有挑战性的现实世界系统中测试量子化学模型，这些系统具有分子内和分子间相互作用之间的复杂相互作用，其中一些受到离域误差的显著影响。
Conformational polymorphs of organic molecular crystals represent a challenging test for quantum chemistry because they require careful balancing of the intra- and intermolecular interactions. This study examines 54 molecular conformations from 20 sets of conformational polymorphs, along with the relative lattice energies and 173 dimer interactions taken from six of the polymorph sets. These systems are studied with a variety of van der Waals-inclusive density functionals theory models; dispersion-corrected spin-component-scaled second-order MOller-Plesset perturbation theory (SCS-MP2D); and domain local pair natural orbital coupled cluster singles, doubles, and perturbative triples [DLPNO-CCSD(T)]. We investigate how delocalization error in conventional density functionals impacts monomer conformational energies, systematic errors in the intermolecular interactions, and the nature of error cancellation that occurs in the overall crystal. The density functionals B86bPBE-XDM, PBE-D4, PBE-MBD, PBE0-D4, and PBE0-MBD are found to exhibit sizable one-body and two-body errors vs DLPNO-CCSD(T) benchmarks, and the level of success in predicting the relative polymorph energies relies heavily on error cancellation between different types of intermolecular interactions or between intra- and intermolecular interactions. The SCS-MP2D and, to a lesser extent, omega B97M-V models exhibit smaller errors and rely less on error cancellation. Implications for crystal structure prediction of flexible compounds are discussed. Finally, the one-body and two-body DLPNO-CCSD(T) energies taken from these conformational polymorphs establish the CP1b and CP2b benchmark datasets that could be useful for testing quantum chemistry models in challenging real-world systems with complex interplay between intra- and intermolecular interactions, a number of which are significantly impacted by delocalization error.