Sensitivity of coupled cluster electronic properties on the reference determinant: Can Kohn–Sham orbitals be more beneficial than Hartree–Fock orbitals?,Journal of Computational Chemistry

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Sensitivity of coupled cluster electronic properties on the reference determinant: Can Kohn–Sham orbitals be more beneficial than Hartree–Fock orbitals?
Journal of Computational Chemistry ( IF 3.4 ) Pub Date : 2022-10-05 , DOI: 10.1002/jcc.26996
Zsolt Benedek _{1,

2,

3} , Paula Timár _{1,

2} , Tibor Szilvási ₃ , Gergely Barcza _{1,

3,

4}

Affiliation

Coupled cluster calculations are traditionally performed over Hartree–Fock reference orbitals (HF-CC methodology). However, in the literature it has been repeatedly raised whether the use of a Kohn–Sham reference (KS-CC methodology) might result in improved performance relative to HF-CC. In the present study, we re-examine the relation of HF-CC and KS-CC methods by comparing the results of widely applied truncated CC calculations (CCSD, CCSD(T), CCSDT) to the limit of full configuration interaction (FCI), which serves as an undebatable reference point of accuracy. Based on a series of CC calculations on diatoms and transition metal complexes, we demonstrate that no systematic improvement of coupled cluster electronic energies, densities and chemical reaction energies is expected when changing from HF to a KS reference. Nevertheless, fortuitous error cancellations might occasionally result in illusory improvement compared to HF-CC. Altogether, the application of KS-CC is not advantageous over HF-CC, but it is also not unreasonable as the choice of reference has negligible influence on the results at sufficiently high CC levels. In addition, KS-CC can be a particularly useful alternative if difficulties are encountered in HF or HF-CC convergence. It is also notable that KS-CC results are found to be practically independent of the chosen density functional, which implies that almost any KS-CC method can be used in place of HF-CC.

中文翻译：

耦合簇电子特性对参考行列式的敏感性：Kohn-Sham 轨道能否比 Hartree-Fock 轨道更有益？

耦合簇计算传统上是在 Hartree–Fock 参考轨道上执行的（HF-CC 方法）。然而，在文献中反复提出使用 Kohn-Sham 参考（KS-CC 方法）是否会导致相对于 HF-CC 的性能改进。在本研究中，我们通过将广泛应用的截断 CC 计算（CCSD、CCSD(T)、CCSDT）的结果与完全配置交互 (FCI) 的极限进行比较，重新审视 HF-CC 和 KS-CC 方法的关系, 作为无可争议的准确性参考点。基于对硅藻和过渡金属配合物的一系列 CC 计算，我们证明当从 HF 变为 KS 参考时，耦合团簇电子能、密度和化学反应能的系统性改善是预期的。尽管如此，与 HF-CC 相比，偶然的错误取消可能偶尔会导致虚幻的改进。总而言之，KS-CC 的应用并不优于 HF-CC，但它也并非不合理，因为在足够高的 CC 水平下，参考的选择对结果的影响可以忽略不计。此外，如果在 HF 或 HF-CC 收敛中遇到困难，KS-CC 可能是一个特别有用的替代方案。还值得注意的是，发现 KS-CC 结果实际上与所选的密度泛函无关，这意味着几乎任何 KS-CC 方法都可以用来代替 HF-CC。但这也不是不合理的，因为在足够高的 CC 水平下，参考的选择对结果的影响可以忽略不计。此外，如果在 HF 或 HF-CC 收敛中遇到困难，KS-CC 可能是一个特别有用的替代方案。还值得注意的是，发现 KS-CC 结果实际上与所选的密度泛函无关，这意味着几乎任何 KS-CC 方法都可以用来代替 HF-CC。但这也不是不合理的，因为在足够高的 CC 水平下，参考的选择对结果的影响可以忽略不计。此外，如果在 HF 或 HF-CC 收敛中遇到困难，KS-CC 可能是一个特别有用的替代方案。还值得注意的是，发现 KS-CC 结果实际上与所选的密度泛函无关，这意味着几乎任何 KS-CC 方法都可以用来代替 HF-CC。

更新日期：2022-10-05

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