基于哈特里-福克对称适配扰动理论的 -D3 和 -D4 弥散模型的阻尼函数参数优化

Austin M. Wallace, C. David Sherrill
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摘要

对称性调整扰动理论(SAPT)直接计算分子间相互作用的静电、交换-斥力、感应/极化和伦敦色散成分的能量。在基于哈特里-福克("SAPT0")或密度泛函理论的 SAPT 中,最耗时的步骤是计算色散项。之前的工作已经探索了用简单的阻尼渐近模型来替代这些昂贵的分散项。我们最近研究了[Schriber 等人,J. Chem. Phys. 154, 234107 (2021)]用 Grimme 流行的 -D3 修正取代 SAPT0 的色散项时的精度,将计算成本从 O(N5) 缩减到 O(N3)。该研究利用在 8299 个二聚体数据集上对耦合簇完整基集极限 [CCSD(T)/CBS] 的估计,优化了 SAPT0-D3/jun-cc-pVDZ 的阻尼函数参数。在此,我们探索了使用额外基集的 SAPT0-D3 以及使用 -D4 的类似模型的准确性。阻尼参数对基集并不敏感,由此得到的 SAPT0-D 模型平均总相互作用能比 SAPT0 更准确。我们的结果在以下几个方面令人惊讶:(1)对于这些系统,-D4 相对于-D3 的改进可以忽略不计,即使是带电系统,-D4 原则上也应该更加精确;(2)对于三体弥散,添加 Axilrod-Teller-Muto 项并不能改善该测试集的误差统计;(3)对于总相互作用能,SAPT0-D 甚至比基于 aug-cc-pVDZ 基础的、计算成本更高的密度泛函理论 SAPT [SAPT(DFT)]更加精确。不过,SAPT0 和 SAPT0-D3/D4 的相互作用能得益于交换项和弥散项之间的显著误差抵消。
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Optimization of damping function parameters for -D3 and -D4 dispersion models for Hartree–Fock based symmetry-adapted perturbation theory
Symmetry-adapted perturbation theory (SAPT) directly computes intermolecular interaction energy in terms of electrostatics, exchange-repulsion, induction/polarization, and London dispersion components. In SAPT based on Hartree–Fock (“SAPT0”) or based on density functional theory, the most time-consuming step is the computation of the dispersion terms. Previous work has explored the replacement of these expensive dispersion terms with simple damped asymptotic models. We recently examined [Schriber et al. J. Chem. Phys. 154, 234107 (2021)] the accuracy of SAPT0 when replacing its dispersion term with Grimme’s popular -D3 correction, reducing the computational cost scaling from O(N5) to O(N3). That work optimized damping function parameters for SAPT0-D3/jun-cc-pVDZ using estimates of the coupled-cluster complete basis set limit [CCSD(T)/CBS] on a 8299 dimer dataset. Here, we explore the accuracy of SAPT0-D3 with additional basis sets, along with an analogous model using -D4. Damping parameters are rather insensitive to basis sets, and the resulting SAPT0-D models are more accurate on average for total interaction energies than SAPT0. Our results are surprising in several respects: (1) improvement of -D4 over -D3 is negligible for these systems, even charged systems where -D4 should, in principle, be more accurate; (2) addition of Axilrod–Teller–Muto terms for three-body dispersion does not improve error statistics for this test set; and (3) SAPT0-D is even more accurate on average for total interaction energies than the much more computationally costly density functional theory based SAPT [SAPT(DFT)] in an aug-cc-pVDZ basis. However, SAPT0 and SAPT0-D3/D4 interaction energies benefit from significant error cancellation between exchange and dispersion terms.
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