论文标题

用量子蒙特卡洛评估化合物形成能的准确性

Assessing the accuracy of compound formation energies with quantum Monte Carlo

论文作者

Isaacs, Eric B., Shin, Hyeondeok, Annaberdiyev, Abdulgani, Wolverton, Chris, Mitas, Lubos, Benali, Anouar, Heinonen, Olle

论文摘要

准确地预测化合物的形成能(描述其热力学稳定性)是材料物理学的关键挑战。在这里,我们采用具有单参考试验功能的多体量子蒙特卡洛(QMC)来计算两种电子上不同化合物的形成能,金属间的VPT $ _2 $和半导体CUI,用于使用标准密度功能(DFT),使用标准密度功能(DFT)预测,并使用Perdew-Berke Ernzer(perdew-bylke Ernzer)(Perdew)(dft)预测(dft)(dft)功能近似明显偏离可用的实验值。对于VPT $ _2 $,我们发现QMC,SCAN和PBE0估算之间的协议,因此与放热实验值少得多。对于CUI而言,QMC结果既不符合扫描,也不同意PBE指向DFT交换相关偏见,这可能与局部Cu $ 3D $电子有关。与DFT中某些密度功能近似的行为相比,与实验相比,自旋平均QMC的QMC表现出较小但仍然明显的偏差。通过合并CUI和固体I $ _2 $的自旋轨道校正来稍微改善QMC结果,从而使实验和理论在约120 〜MEV/ATOM内不完善但合理的一致性。

Accurately predicting the formation energy of a compound, which describes its thermodynamic stability, is a key challenge in materials physics. Here, we employ many-body quantum Monte Carlo (QMC) with single-reference trial functions to compute the formation energy of two electronically disparate compounds, the intermetallic VPt$_2$ and the semiconductor CuI, for which standard density functional theory (DFT) predictions using both the Perdew-Burke Ernzerhof (PBE) and the strongly constrained and appropriately normed (SCAN) density functional approximations deviate markedly from available experimental values. For VPt$_2$, we find an agreement between QMC, SCAN, and PBE0 estimates, which therefore remain in disagreement with the much less exothermic experimental value. For CuI, the QMC result agrees with neither SCAN nor PBE pointing towards DFT exchange-correlation biases, likely related to the localized Cu $3d$ electrons. Compared to the behavior of some density functional approximations within DFT, spin-averaged QMC exhibits a smaller but still appreciable deviation when compared to experiment. The QMC result is slightly improved by incorporating spin-orbit corrections for CuI and solid I$_2$, so that experiment and theory are brought into imperfect but reasonable agreement within about 120~meV/atom.

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