Schubert Yannick, Luber Sandra, Marzari Nicola, Linscott Edward
Department of Chemistry, University of Zurich, 8057 Zurich, Switzerland.
Theory and Simulations of Materials (THEOS) and National Centre for Computational Design and Discovery of Novel Materials (MARVEL), École Polytechnique Fédérale de Lausanne, 1015 Lausanne, Switzerland.
NPJ Comput Mater. 2024;10(1):299. doi: 10.1038/s41524-024-01484-3. Epub 2024 Dec 20.
Koopmans spectral functionals are a powerful extension of Kohn-Sham density-functional theory (DFT) that enables the prediction of spectral properties with state-of-the-art accuracy. The success of these functionals relies on capturing the effects of electronic screening through scalar, orbital-dependent parameters. These parameters have to be computed for every calculation, making Koopmans spectral functionals more expensive than their DFT counterparts. In this work, we present a machine-learning model that-with minimal training-can predict these screening parameters directly from orbital densities calculated at the DFT level. We show in two prototypical use cases that using the screening parameters predicted by this model, instead of those calculated from linear response, leads to orbital energies that differ by less than 20 meV on average. Since this approach dramatically reduces run times with minimal loss of accuracy, it will enable the application of Koopmans spectral functionals to classes of problems that previously would have been prohibitively expensive, such as the prediction of temperature-dependent spectral properties. More broadly, this work demonstrates that measuring violations of piecewise linearity (i.e., curvature in total energies with respect to occupancies) can be done efficiently by combining frozen-orbital approximations and machine learning.
库普曼斯谱泛函是科恩-沙姆密度泛函理论(DFT)的一种强大扩展,能够以最先进的精度预测光谱性质。这些泛函的成功依赖于通过标量、轨道依赖参数来捕捉电子屏蔽效应。这些参数必须针对每次计算进行计算,这使得库普曼斯谱泛函比其DFT对应物成本更高。在这项工作中,我们提出了一种机器学习模型,该模型只需最少的训练就能直接根据在DFT水平计算出的轨道密度预测这些屏蔽参数。我们在两个典型用例中表明,使用该模型预测的屏蔽参数,而不是从线性响应计算出的参数,会导致轨道能量平均差异小于20毫电子伏特。由于这种方法在精度损失最小的情况下显著减少了运行时间,它将使库普曼斯谱泛函能够应用于以前成本过高的各类问题,例如温度依赖光谱性质的预测。更广泛地说,这项工作表明,通过结合冻结轨道近似和机器学习,可以有效地测量分段线性的违反情况(即总能量相对于占据数的曲率)。