Departament de Ciència de Materials i Química Física & Institut de Química Teòrica i Computacional (IQTCUB), Universitat de Barcelona, C/Martí i Franquès 1, 08028 Barcelona, Spain.
Department of Chemistry, University of North Texas, Denton, Texas 76203-5017, USA.
J Chem Phys. 2017 Jul 14;147(2):024106. doi: 10.1063/1.4991833.
We use a total energy difference approach to explore the ability of various density functional theory based methods in accounting for the differential effect of static electron correlation on the C(1s) and O(1s) core level binding energies (BEs) of the CO molecule. In particular, we focus on the magnitude of the errors of the computed C(1s) and O(1s) BEs and on their relative difference as compared to experiment and to previous results from explicitly correlated wave functions. Results show that the different exchange-correlation functionals studied here behave rather erratically and a considerable number of them lead to large errors in the BEs and/or the BE shifts. Nevertheless, the TPSS functional, its TPSSm and RevTPSS derivations, and its corresponding hybrid counterpart, TPSSh, perform better than average and provide BEs and BE shifts in good agreement with experiment.
我们采用总能量差方法来研究各种基于密度泛函理论的方法在描述静态电子相关对 CO 分子的 C(1s)和 O(1s)芯能级结合能 (BE) 的差分效应的能力。特别关注计算的 C(1s)和 O(1s) BE 的误差大小，以及与实验和先前来自显式相关波函数的结果的相对差异。结果表明，这里研究的不同交换相关泛函表现相当不稳定，其中相当数量的泛函导致 BE 和/或 BE 位移出现较大误差。然而，TPSS 泛函、其 TPSSm 和 RevTPSS 衍生泛函以及相应的混合泛函 TPSSh 的表现优于平均水平，提供的 BE 和 BE 位移与实验结果吻合较好。
