Regional Embedding Enables High-Level Quantum Chemistry for Surface Science
Regional Embedding Enables High-Level Quantum Chemistry for Surface Science
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DOI：
10.1021/acs.jpclett.0c03274
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发表时间：
2021-01-21
影响因子：
5.7
通讯作者：
Berkelbach, Timothy C.
中科院分区：
文献类型：
--
作者：
Lau, Bryan T. G.;Knizia, Gerald;Berkelbach, Timothy C.
与普通密度泛函相比，从头算波函数方法可以提供更高的可靠性和准确性，这可能被证明是有用的，当建模吸附或其他周期性系统的缺陷。然而，平移对称性的破缺需要大的超原胞，这对于相关波函数方法来说通常是禁止的。作为一种替代方案，本文介绍了区域嵌入的方法，它使相关的波函数治疗只有一个目标片段的利益，通过小，片段局部轨道空间构造使用一个简单的重叠标准。水在氢化锂、六方氮化硼和石墨烯基底上吸附的应用表明，区域嵌入与焦点校正相结合可以以非常小的碎片尺寸提供收敛的CCSD（T）（耦合簇）吸附能。
Compared to common density functionals, ab initio wave function methods can provide greater reliability and accuracy, which could prove useful when modeling adsorbates or A defects of otherwise periodic systems. However, the breaking of translational symmetry necessitates large supercells that are often prohibitive for correlated wave function methods. As an alternative, this paper introduces the regional embedding approach, which enables correlated wave function treatments of only a target fragment of interest through small, fragment-localized orbital spaces constructed using a simple overlap criterion. Applications to the adsorption of water on lithium hydride, hexagonal boron nitride, and graphene substrates show that regional embedding combined with focal-point corrections can provide converged CCSD(T) (coupled-cluster) adsorption energies with very small fragment sizes.