Department of Chemistry , University of Minnesota , 207 Pleasant St. SE , Minneapolis , Minnesota 55455 , United States.
J Chem Theory Comput. 2018 Apr 10;14(4):1928-1942. doi: 10.1021/acs.jctc.7b01154. Epub 2018 Mar 20.
We present a level shift projection operator-based embedding method for systems with periodic boundary conditions-where the "active" subsystem can be described using either density functional theory (DFT) or correlated wave function (WF) methods and the "environment" is described using DFT. Our method allows for k-point sampling, is shown to be exactly equal to the canonical DFT solution of the full system under the limit that we use the full system basis to describe each subsystem, and can treat the active subsystem either with periodic boundary conditions-in what we term "periodic-in-periodic" embedding-or as a molecular cluster-in "cluster-in-periodic" embedding. We explore each of these methods and show that cluster WF-in-periodic DFT embedding can accurately calculate the absorption energy of CO on to a Si(100)-2×1 surface.
我们提出了一种基于能级移动投影算子的嵌入方法，用于具有周期性边界条件的系统——其中“活性”子系统可以使用密度泛函理论（DFT）或相关波函数（WF）方法来描述，而“环境”则使用 DFT 来描述。我们的方法允许进行 k 点采样，在我们使用全系统基组来描述每个子系统的极限下，它被证明与全系统的正则 DFT 解完全相等，并且可以用周期性边界条件处理活性子系统——我们称之为“周期性内嵌入”，或者作为分子团簇——“团簇内嵌入”。我们探索了这些方法中的每一种，并表明团簇 WF 内周期性 DFT 嵌入可以准确地计算 CO 在 Si(100)-2×1 表面上的吸收能。
