Bond-Valence Parameterization for the Accurate Description of DFT Energetics
Bond-Valence Parameterization for the Accurate Description of DFT Energetics
复制标题
用于准确描述 DFT 能量学的键价参数化
DOI：
10.1021/acs.jctc.1c01113
复制
发表时间：
2022
影响因子：
5.5
通讯作者：
Musgrave, Charles B.
中科院分区：
文献类型：
--
作者：
Morelock, Ryan J.;Bare, Zachary J.;Musgrave, Charles B.
我们报告了一个键价方法（BVM）参数化框架，捕获密度泛函理论（DFT）计算的相对稳定性，使用BVM全局不稳定性指数（GII）。我们将我们的框架与188个实验观察到的ABO3钙钛矿氧化物的数据集进行了基准测试，每个氧化物都是在11个独特的格雷泽八面体倾斜系统中生成的，并使用DFT进行了优化。我们的约束最小化程序最大限度地减少了GII的188钙钛矿基态结构预测的DFT，同时强制执行GII和DFT能量之间的线性相关性的所有2068竞争结构。基于使用我们的框架确定的BVM参数的GII正确地识别了188种组合物中的135种中的DFT基态钙钛矿结构或188种组合物中的152种中的两种最低能量结构之一。使用最常见的方法来参数化BVM，最大限度地减少BVM站点差异因子的均方根偏差，GII正确地识别了188种组合物中仅41种的DFT基态钙钛矿结构。因此，我们的新的参数化框架是一个显着的改进，现有的程序和重要的第一步BVM为基础的结构生成协议，重现DFT。
We report a bond-valence method (BVM) parameterization framework that captures density functional theory (DFT)-computed relative stabilities using the BVM global instability index (GII). We benchmarked our framework against a dataset of 188 experimentally observed ABO3perovskite oxides, each of which was generated in 11 unique Glazer octahedral tilt systems and optimized using DFT. Our constrained minimization procedure minimizes the GIIs of the 188 perovskite ground state structures predicted by DFT while enforcing a linear correlation between the GIIs and DFT energies of all 2068 competing structures. GIIs based on BVM parameters determined using our framework correctly identified the DFT ground state perovskite structure in 135 of 188 compositions or one of the two lowest energy structures in 152 of 188 compositions. Using the most common approach to parameterize BVM, which minimizes the root-mean-square deviation of the BVM site discrepancy factors, GIIs correctly identified the DFT ground state perovskite structure in only 41 of 188 compositions. Our new parameterization framework is therefore a marked improvement over the existing procedure and an important first step toward BVM-based structure generation protocols that reproduce DFT.