Improving the precision of work-function calculations within plane-wave density functional theory

IF 2.9 Q3 CHEMISTRY, PHYSICAL
Yiyuan Wang, Sari J Laihonen, Mikael Unge, Arash A Mostofi
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Abstract

Work function is a fundamental property of metals and is related to many surface-related phenomena of metals. Theoretically, it can be calculated with a metal slab supercell in density functional theory (DFT) calculations. In this paper, we discuss how the commensurability of atomic structure with the underlying fast Fourier transform (FFT) grid affects the accuracy of work function obtained from plane-wave pseudopotential DFT calculations. We show that the macroscopic average potential, which is an important property in work function calculations under the ‘bulk reference’ method, is more numerically stable when it is calculated with commensurate FFT grids than with incommensurate FFT grids. Due to the stability of the macroscopic average potential, work function calculated with commensurate FFT grids shows better convergence with respect to basis set size, vacuum length and slab thickness of a slab supercell. After we control the FFT grid commensurability issue in our work function calculations, we obtain well-converged work functions for Al, Pd, Au and Pt of (100), (110) and (111) surface orientations. For all the metals considered, the ordering of our calculated work functions of the three surface orientations agrees with experiment. Our findings reveal the importance of the FFT grid commensurability issue, which is usually neglected in practice, in obtaining accurate metal work functions, and are also meaningful to other DFT calculations which can be affected by the FFT grid commensurability issue.
提高平面波密度泛函理论功函数计算的精度
功函数是金属的一项基本性质,与金属的许多表面现象有关。理论上,它可以通过密度泛函理论(DFT)计算中的金属板坯超级单元来计算。本文讨论了原子结构与底层快速傅立叶变换(FFT)网格的可比性如何影响平面波伪势 DFT 计算所获得的功函数的精度。我们的研究表明,宏观平均电势是 "体基准 "方法功函数计算中的一个重要属性,与不相称的 FFT 网格相比,用相称的 FFT 网格计算的宏观平均电势在数值上更加稳定。由于宏观平均电势的稳定性,使用相称 FFT 网格计算的功函数在板坯超级电池的基集大小、真空长度和板坯厚度方面表现出更好的收敛性。在功函数计算中控制了 FFT 网格的可比性问题后,我们得到了表面取向为 (100)、(110) 和 (111) 的铝、钯、金和铂的收敛性良好的功函数。对于所考虑的所有金属,我们计算出的三种表面取向的功函数排序与实验结果一致。我们的研究结果揭示了在实践中通常被忽视的 FFT 网格可比性问题对获得精确金属功函数的重要性,同时对可能受 FFT 网格可比性问题影响的其他 DFT 计算也很有意义。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
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来源期刊
CiteScore
3.70
自引率
11.50%
发文量
46
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