论文标题

通过提高密度改善结果:密度校正的密度功能理论

Improving results by improving densities: Density-corrected density functional theory

论文作者

Sim, Eunji, Song, Suhwan, Vuckovic, Stefan, Burke, Kieron

论文摘要

DFT计算在化学和材料中都变得广泛,因为它们通常以比基于波函数的方法低得多的计算成本提供了有用的准确性。所有实用的DFT计算都需要与未知的交换相关能量进行近似,然后在Kohn-Sham方案中自愿使用,以从近似密度产生近似能量。密度校正的DFT仅仅是对总能量误差的相对贡献的研究。在绝大多数DFT计算中,由于密度近似密度引起的误差可以忽略不计。但是,由于某些类别的功能将其应用于某些类别的问题,密度误差足够大,以至于有助于能量,并且其去除会导致更好的结果。这些问题包括反应屏障,涉及$π$ - 缀合的扭转障碍,卤素键,自由基和阴离子,大多数拉伸键等。在所有情况下,使用更准确的密度可显着提高性能,并且通常使用Hartree-Fock密度的简单权宜之计。本文解释了什么是DC-DFT,可能会改善结果以及DC-DFT如何产生更准确的功能。我们还概述了该领域的挑战和前景。

DFT calculations have become widespread in both chemistry and materials, because they usually provide useful accuracy at much lower computational cost than wavefunction-based methods. All practical DFT calculations require an approximation to the unknown exchange-correlation energy, which is then used self-consistently in the Kohn-Sham scheme to produce an approximate energy from an approximate density. Density-corrected DFT is simply the study of the relative contributions to the total energy error. In the vast majority of DFT calculations, the error due to the approximate density is negligible. But with certain classes of functionals applied to certain classes of problems, the density error is sufficiently large as to contribute to the energy noticeably, and its removal leads to much better results. These problems include reaction barriers, torsional barriers involving $π$-conjugation, halogen bonds, radicals and anions, most stretched bonds, etc. In all such cases, use of a more accurate density significantly improves performance, and often the simple expedient of using the Hartree-Fock density is enough. This article explains what DC-DFT is, where it is likely to improve results, and how DC-DFT can produce more accurate functionals. We also outline challenges and prospects for the field.

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