论文标题

使用平面波将耦合簇理论的局部嵌入到随机相近似中

Local embedding of Coupled Cluster theory into the Random Phase Approximation using plane-waves

论文作者

Schäfer, Tobias, Libisch, Florian, Kresse, Georg, Grüneis, Andreas

论文摘要

我们提出了一种在周期性环境中处理局部电子相关效应的嵌入方法。在单个一致的框架中,我们的基于平面波的方案将使用局部轨道的局部高级相关计算(此处耦合群集理论,CC)嵌入到低级相关计算中(此处直接随机相位近似,RPA)。这种选择允许对远程分散效应进行准确效率的处理。如果低水平和高级长距离色散在定量上相似,则可以观察到相对于局部片段大小的加速收敛性,就像RPA中的CC一样。为了证明引入的嵌入方法的能力,我们计算了表面和奇巴兹晶体笼子上分子的吸附能,以及在固体中固体中晶格杂质的形成能在高度准确的多种电子扰动理论的水平上。例如,在CC水平上,甲烷分子在沸石甲虫中的吸收能的误差低于20 MeV。作为我们最大的周期性基准系统,我们将方案应用于在包含1000多个电子的超级细胞中水分子在二氧化钛上的吸附。

We present an embedding approach to treat local electron correlation effects in periodic environments. In a single, consistent framework, our plane-wave based scheme embeds a local high-level correlation calculation (here Coupled Cluster Theory, CC), employing localized orbitals, into a low-level correlation calculation (here the direct Random Phase Approximation, RPA). This choice allows for an accurate and effcient treatment of long-range dispersion effects. Accelerated convergence with respect to the local fragment size can be observed if the low-level and high-level long-range dispersion are quantitatively similar, as is the case for CC in RPA. To demonstrate the capabilities of the introduced embedding approach, we calculate adsorption energies of molecules on a surface and in a chabazite crystal cage, as well as the formation energy of a lattice impurity in a solid at the level of highly accurate many-electron perturbation theories. The absorption energy of a methane molecule in a zeolite chabazite, for instance, is converged with an error well below 20 meV at the CC level. As our largest periodic benchmark system, we apply our scheme to the adsorption of a water molecule on titania in a supercell containing more than 1000 electrons.

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