The performance of exchange-correlation functionals in density-functional theory (DFT) calculations for liquid metal has not been sufficiently examined. In the present study, benchmark tests of Perdew-Burke-Ernzerhof (PBE), Armiento-Mattsson 2005 (AM05), PBE re-parameterized for solids, and local density approximation (LDA) functionals are conducted for liquid sodium. The pair correlation function, equilibrium atomic volume, bulk modulus, and relative enthalpy are evaluated at 600 K and 1000 K. Compared with the available experimental data, the errors range from −11.2% to 0.0% for the atomic volume, from −5.2% to 22.0% for the bulk modulus, and from −3.5% to 2.5% for the relative enthalpy depending on the DFT functional. The generalized gradient approximation functionals are superior to the LDA functional, and the PBE and AM05 functionals exhibit the best performance. In addition, we assess whether the error tendency in liquid simulations is comparable to that in solid simulations, which would suggest that the atomic volume and relative enthalpy performances are comparable between solid and liquid states but that the bulk modulus performance is not. These benchmark test results indicate that the results of liquid simulations are significantly dependent on the exchange-correlation functional and that the DFT functional performance in solid simulations can be used to roughly estimate the performance in liquid simulations.

中文翻译：

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液态金属密度泛函理论计算中交换相关泛函的性能：钠的基准测试

液体金属的密度泛函理论（DFT）计算中交换相关泛函的性能尚未得到充分检验。在本研究中，Perdew-Burke-Ernzerhof（PBE），Armiento-Mattsson 2005（AM05）的基准测试，对固体进行重新参数化的PBE以及对液体钠的局部密度近似（LDA）功能进行了测试。在600 K和1000 K时评估了对相关函数，平衡原子体积，体积模量和相对焓。与可用的实验数据相比，原子体积的误差范围从-11.2％到0.0％，从-5.2％取决于DFT的功能，其体积模量为22.0％，相对焓为-3.5％至2.5％。广义梯度逼近泛函优于LDA泛函，PBE和AM05功能表现出最佳性能。此外，我们评估了液体模拟中的误差趋势是否可与固体模拟中的误差趋势相媲美，这表明在固态和液态之间原子体积和相对焓性能可比，但体积模量性能却不可。这些基准测试结果表明，液体模拟的结果在很大程度上取决于交换相关函数，并且固体模拟中的DFT功能性能可以用来大致估计液体模拟中的性能。这表明在固态和液态之间原子体积和相对焓性能是可比的，但体积模量性能却不高。这些基准测试结果表明，液体模拟的结果很大程度上取决于交换相关函数，并且固体模拟中的DFT功能性能可以用来大致估计液体模拟中的性能。这表明在固态和液态之间原子体积和相对焓性能是可比的，但体积模量性能却不高。这些基准测试结果表明，液体模拟的结果很大程度上取决于交换相关函数，并且固体模拟中的DFT功能性能可以用来大致估计液体模拟中的性能。