Karton Amir
School of Science and Technology, University of New England, Armidale, NSW 2351, Australia.
Phys Chem Chem Phys. 2024 May 22;26(20):14594-14606. doi: 10.1039/d4cp00387j.
Total atomization energies (TAEs) are a central quantity in density functional theory (DFT) benchmark studies. However, so far TAE databases obtained from experiment or high-level wavefunction theory included up to hundreds of TAEs. Here, we use the GDB-9 database of 133k CCSD(T) TAEs generated by Curtiss and co-workers [B. Narayanan, P. C. Redfern, R. S. Assary and L. A. Curtiss, , 2019, , 7449] to evaluate the performance of 14 representative DFT methods across the rungs of Jacob's ladder (namely, PBE, BLYP, B97-D, M06-L, τ-HCTH, PBE0, B3LYP, B3PW91, ωB97X-D, τ-HCTHh, PW6B95, M06, M06-2X, and MN15). We first use the [PBE] diagnostic for nondynamical correlation to eliminate systems that potentially include significant multireference effects, for which the CCSD(T) TAEs might not be sufficiently reliable. The resulting database (denoted by GDB9-nonMR) includes 122k species. Of the considered functionals, B3LYP attains the best performance relative to the G4(MP2) reference TAEs, with a mean absolute deviation (MAD) of 4.09 kcal mol. This first-generation hybrid functional, in which the three mixing coefficients were fitted against a small set of TAEs, is one of the few functionals that are not systematically biased towards overestimating the G4(MP2) TAEs, as demonstrated by a mean-signed deviation (MSD) of 0.45 kcal mol. The relatively good performance of B3LYP is followed by the heavily parameterized M06-L -GGA functional, which attains a MAD of 6.24 kcal mol. The PW6B95, M06, M06-2X, and MN15 functionals tend to systematically overestimate the G4(MP2) TAEs and attain MADs ranging between 18.69 (M06) and 28.54 (MN15) kcal mol. However, PW6B95 and M06-2X exhibit particularly narrow error distributions. Thus, scaling their TAEs by an empirical scaling factor reduces their MADs to merely 3.38 (PW6B95) and 2.85 (M06-2X) kcal mol. Empirical dispersion corrections (, D3 and D4) are attractive, and therefore, their inclusion worsens the performance of methods that systematically overestimate the TAEs.
总原子化能（TAEs）是密度泛函理论（DFT）基准研究中的核心量。然而，到目前为止，从实验或高水平波函数理论获得的TAE数据库包含多达数百个TAEs。在这里，我们使用由柯蒂斯及其同事生成的133k个CCSD(T) TAE的GDB - 9数据库[B. 纳拉亚南、P. C. 雷德费恩、R. S. 阿萨里和L. A. 柯蒂斯，，2019，，7449]来评估雅各布天梯各层级上14种代表性DFT方法的性能（即PBE、BLYP、B97 - D、M06 - L、τ - HCTH、PBE0、B3LYP、B3PW91、ωB97X - D、τ - HCTHh、PW6B95、M06、M06 - 2X和MN15）。我们首先使用[PBE]非动态相关诊断来排除可能包含显著多参考效应的体系，对于这些体系，CCSD(T) TAE可能不够可靠。所得数据库（记为GDB9 - nonMR）包含122k个物种。在所考虑的泛函中，相对于G4(MP2)参考TAE，B3LYP表现最佳，平均绝对偏差（MAD）为4.09 kcal/mol。这种第一代杂化泛函，其三个混合系数是针对一小部分TAE拟合的，是少数几种不会系统性地偏向高估G4(MP2) TAE的泛函之一，平均符号偏差（MSD）为0.45 kcal/mol就证明了这一点。B3LYP相对较好的性能之后是参数化程度很高的M06 - L - GGA泛函，其MAD为6.24 kcal/mol。PW6B95、M06、M06 - 2X和MN15泛函往往会系统性地高估G4(MP2) TAE，MAD在介于18.69（M06）和28.54（MN15）kcal/mol之间。然而，PW6B95和M06 - 2X表现出特别窄的误差分布。因此，通过经验缩放因子对它们的TAE进行缩放，可将其MAD分别降至仅3.38（PW6B95）和2.85（M06 - 2X）kcal/mol。经验色散校正（如D3和D4）很有吸引力，因此，将它们包含在内会使系统性高估TAE的方法的性能变差。
