发表机构
Universidad Autónoma Metropolitana-Iztapalapa; University of Florida; Ball State University（墨西哥自治大学伊察帕拉帕分校; 佛罗里达大学; 鲍尔州立大学）
机构由 AI 辅助整理，请以论文原文为准。AI 中文总结
本研究评估了LAK meta-GGA在分子性质上的表现，发现其与r2SCAN相当，但不如混合泛函；NCAPR GGA的导数不连续性修正能更准确地估计基本带隙和满足IP定理。
AI 中文摘要
使用 Kohn-Sham 本征值间隙（最高占据分子轨道到最低未占据分子轨道，HOMO-LUMO）作为基本带隙（I-A，I=电离势，A=电子亲和能）的估计器，对于相对简单的交换关联泛函（如 meta-GGA）来说是一个长期存在的挑战。LAK meta-GGA [T. Lebeda 等人，Phys. Rev. Lett. 133, 136402 (2024)] 的开发旨在强调某些约束条件，以使 LAK KS 间隙接近 HSE06 混合泛函 [A.V. Krudau 等人，J. Chem. Phys. 125, 224106 (2006)] 的间隙。LAK 泛函仅针对一个小型原子化数据集和一个非常小的键长数据集进行了测试，没有进行分子 HOMO-LUMO 间隙测试。在此，我们针对广泛使用的大型参考数据集（包括分子生成热、键长、谐振频率、I 和 A）对 LAK 进行测试，并与 r2SCAN [J.W. Furness 等人，J. Phys. Chem. Lett. 11, 8208 (2020)] 以及 HSE06 和 PBE0（一种截然不同的混合泛函）进行比较。在这些测试中，LAK 在几何结构、生成热、HOMO-LUMO 间隙或 DFT IP 定理满足度方面并未比 r2SCAN 有显著改善。与实验 I 和 A 值相比，情况相同；LAK 结果类似于 r2SCAN 结果，而非 HSE06。此外，由 NCAPR GGA [J. Carmona-Espindola 等人，J. Chem. Phys. 157, 114109 (2022)] 作为导数不连续性估计生成的 HOMO 和 LUMO 位移，将裸 NCAPR HOMO 和 LUMO 本征值修正为与实验在基本带隙和 IP 定理方面都比 meta-GGA（LAK、r2SCAN）或混合泛函（HSE、PBE0）有更好的吻合。我们讨论了 LAK 在分子和固体中表现不同的可能原因。
英文摘要
Use of the Kohn-Sham eigenvalue gap (highest occupied molecular orbital to lowest unoccupied, HOMO-LUMO) as a fundamental gap (I-A, I= ionization potential, A= electron affinity) estimator is a long-standing challenge for relatively simple exchange-correlation functionals, e.g. meta-GGAs. The LAK meta-GGA [T. Lebeda et al. Phys. Rev. Lett. 133, 136402 (2024)] was developed to emphasize certain constraints in ways intended to make the LAK KS gaps close to the HSE06 hybrid functional [A.V. Krudau et al. J.Chem. Phys. 125, 224106 (2006)] gaps. The LAK functional was tested against a small atomization data set and a very small bond length set, with no molecular HOMO-LUMO gap testing. Here we test LAK against widely used, large reference data sets for molecular heats of formation, bond lengths, harmonic frequencies, I, and A and compare with r2SCAN [J.W. Furness et al., J. Phys. Chem. Lett. 11, 8208 (2020)] as well as HSE06 and PBE0, a quite different hybrid. On these tests LAK does not give meaningfully better geometries, heats of formation, HOMO-LUMO gaps, or DFT IP theorem satisfaction than r2SCAN. Compared against experimental I and A values the same holds; LAK results resemble r2SCAN results, not HSE06. Moreover, the HOMO and LUMO shifts generated by the NCAPR GGA [J. Carmona-Espindola et al., J. Chem. Phys. 157, 114109 (2022)] as derivative discontinuity estimates, correct the bare NCAPR HOMO and LUMO eigenvalues to substantially better agreement with experiment for both fundamental gap and IP theorem than do the meta-GGAs (LAK, r2SCAN) or hybrids (HSE, PBE0). We discuss possible reasons why LAK behaves differently for molecules and solids.
