Macke Eric, Timrov Iurii, Marzari Nicola, Ciacchi Lucio Colombi
Faculty of Production Engineering, Bremen Center for Computational Materials Science and MAPEX Center for Materials and Processes, Hybrid Materials Interfaces Group, University of Bremen, Am Fallturm 1, 28359 Bremen, Germany.
Theory and Simulation of Materials (THEOS) and National Centre for Computational Design and Discovery of Novel Materials (MARVEL), École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne, Switzerland.
J Chem Theory Comput. 2024 Jun 11;20(11):4824-4843. doi: 10.1021/acs.jctc.3c01403. Epub 2024 May 31.
We present an orbital-resolved extension of the Hubbard correction to density-functional theory (DFT). Compared to the conventional shell-averaged approach, the prediction of energetic, electronic and structural properties is strongly improved, particularly for compounds characterized by both localized and hybridized states in the Hubbard manifold. The numerical values of all Hubbard parameters are readily obtained from linear-response calculations. The relevance of this more refined approach is showcased by its application to bulk solids pyrite (FeS) and pyrolusite (β-MnO), as well as to six Fe(II) molecular complexes. Our findings indicate that a careful definition of Hubbard manifolds is indispensable for extending the applicability of DFT+ beyond its current boundaries. The present orbital-resolved scheme aims to provide a computationally undemanding yet accurate tool for electronic structure calculations of charge-transfer insulators, transition-metal (TM) complexes and other compounds displaying significant orbital hybridization.
我们提出了一种对密度泛函理论（DFT）的哈伯德修正的轨道分辨扩展。与传统的壳层平均方法相比，能量、电子和结构性质的预测有了显著改进，特别是对于在哈伯德流形中具有局域态和杂化态特征的化合物。所有哈伯德参数的数值可通过线性响应计算轻松获得。这种更精细方法的相关性通过其应用于块状固体黄铁矿（FeS）和软锰矿（β-MnO）以及六种Fe(II)分子配合物得到了展示。我们的研究结果表明，仔细定义哈伯德流形对于扩展DFT+超出其当前边界的适用性是必不可少的。目前的轨道分辨方案旨在为电荷转移绝缘体、过渡金属（TM）配合物和其他显示出显著轨道杂化的化合物的电子结构计算提供一种计算要求不高但准确的工具。
