Unconventional Error Cancellation Explains the Success of Hartree–Fock Density Functional Theory for Barrier Heights
Unconventional Error Cancellation Explains the Success of Hartree–Fock Density Functional Theory for Barrier Heights
复制标题
非常规误差消除解释了 Hartree-Fock 势垒高度密度泛函理论的成功
DOI：
10.1021/acs.jpclett.3c03088
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发表时间：
2024
期刊：
影响因子：
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通讯作者：
Perdew, John P.
中科院分区：
文献类型：
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作者：
Kanungo, Bikash;Kaplan, Aaron D.;Shahi, Chandra;Gavini, Vikram;Perdew, John P.
控制化学反应速率的能垒被计算效率高的交换相关能的半局部近似严重低估。半局域密度泛函近似的准确性大大提高了反应势垒的高度，通过评估近似的非自洽的Hartree-Fock电子密度，这已经知道了2030年。传统的解释是，哈特里-福克理论产生更准确的密度。这项工作提出了一个基准的Kohn-Sham反演精确的耦合团簇密度的反应H2+ F → HHF → H + HF，并发现了一个强大的，可以理解的抵消之间的积极（过度校正）密度驱动和大的负功能驱动的错误（预计从拉伸自由基键的过渡态）在这个Hartree-Fock密度泛函理论。这证实了先前的结论（卡普兰，A。D、等人，J. Chem. Theory Comput.2023，19，532 - 543），基于76个势垒高度和三个不太可靠但不太昂贵的完全非局部密度泛函代理，用于精确密度。
Energy barriers, which control the rates of chemical reactions, are seriously underestimated by computationally efficient semilocal approximations for the exchange-correlation energy. The accuracy of a semilocal density functional approximation is strongly boosted for reaction barrier heights by evaluating that approximation non-self-consistently on Hartree–Fock electron densities, which has been known for ∼30 years. The conventional explanation is that the Hartree–Fock theory yields the more accurate density. This work presents a benchmark Kohn–Sham inversion of accurate coupled-cluster densities for the reaction H2+ F → HHF → H + HF and finds a strong, understandable cancellation between positive (excessively overcorrected) density-driven and large negative functional-driven errors (expected from stretched radical bonds in the transition state) within this Hartree–Fock density functional theory. This confirms earlier conclusions (Kaplan, A. D., et al.J. Chem. Theory Comput.2023, 19, 532−543) based on 76 barrier heights and three less reliable, but less expensive, fully nonlocal density functional proxies for the exact density.