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Creating Benchmarks for Lithium Clusters and Using Them for Testing and Validation.
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2024-11-19 , DOI: 10.1021/acs.jctc.4c01224
Maryam Mansoori Kermani,Donald G Truhlar

Metal clusters often have a variety of possible structures, and they are calculated by a wide range of methods; however, fully converged benchmarks on the energy differences of structures and spin states that could be used to test or validate these methods are rare or nonexistent. Small lithium clusters are good candidates for such benchmarks to test different methods against well-converged relative energetics for qualitatively different structures because they have a small number of electrons. The present study provides fully converged benchmarks for Li4 and Li5 clusters and uses them to test a diverse group of approximation methods. To create a dataset of well-converged single-point energies for Li4 and Li5, stationary structures were optimized by Kohn-Sham density functional theory (KS-DFT) and then single-point energy calculations at these structures were carried out by two quite different beyond-CCSD(T) methods. To test other methods single-point energy calculations at these structures were carried out by KS-DFT, Mo̷ller-Plesset (MP) theory, coupled cluster (CC) theory, five composite methods (Gaussian-4, the Wuhan-Minnesota (WM) composite method, and the W2X, W3X, and W3X-L composite methods of Radom and co-workers), multiconfiguration pair-density functional theory (MC-PDFT), complete active space second-order perturbation theory (CASPT2), and n-electron valence state second-order perturbation theory (NEVPT2). Our results show that rhomboid and trigonal bipyramid (TBP) geometries are the most stable structures for Li4 and Li5, respectively. Using the W3X-L method to obtain our best estimates, the mean unsigned deviations were calculated for other methods for several structures and spin states of both Li4 and Li5. Binding energies and M diagnostics were calculated for all structures. The data in this paper are valuable for assessing the reliability of current electronic structure theories and also developing new density functionals and machine learned models.

中文翻译:


为 Lithium 集群创建基准并将其用于测试和验证。



金属团簇通常具有多种可能的结构,并且它们通过多种方法计算;然而,可用于测试或验证这些方法的结构和自旋态能量差异的完全收敛基准很少或不存在。小锂团簇是此类基准的良好候选者,用于针对定性不同的结构测试不同结构的适当收敛相对能量的不同方法,因为它们具有少量电子。本研究为 Li4 和 Li5 集群提供了完全收敛的基准,并使用它们来测试一组不同的近似方法。为了创建 Li4 和 Li5 的收敛良好的单点能量数据集,通过 Kohn-Sham 密度泛函理论 (KS-DFT) 优化了稳态结构,然后通过两种截然不同的 beyond-CCSD(T) 方法对这些结构进行单点能量计算。为了测试其他方法,通过 KS-DFT、Mo̷ller-Plesset (MP) 理论、耦合簇 (CC) 理论、五种复合方法(Gaussian-4、Wuhan-Minnesota (WM) 复合方法以及 Radom 及其同事的 W2X、W3X 和 W3X-L 复合方法)、多构型对密度泛函理论 (MC-PDFT)、完全有源空间二阶微扰理论 (CASPT2) 和 n 电子价态二阶微扰理论(NEVPT2 的)。我们的结果表明,菱形和三角双锥体 (TBP) 几何形状分别是 Li4 和 Li5 最稳定的结构。使用 W3X-L 方法获得我们的最佳估计值,计算了其他方法对 Li4 和 Li5 的几种结构和自旋态的平均无符号偏差。 计算所有结构的结合能和 M 诊断。本文中的数据对于评估当前电子结构理论的可靠性以及开发新的密度泛函和机器学习模型很有价值。
更新日期:2024-11-19
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