论文标题

一般嵌入式群集方案,用于在金属氧化物中准确建模氧空位

General embedded cluster protocol for accurate modeling of oxygen vacancies in metal-oxides

论文作者

Shi, Benjamin Xu, Kapil, Venkat, Zen, Andrea, Chen, Ji, Alavi, Ali, Michaelides, Angelos

论文摘要

o空位(OV)地层能量,$ e_ \ textrm {ov} $,是金属氧化物的重要特性,它管理其在燃料电池或异构催化等应用中的性能。这些缺陷常规研究密度功能理论(DFT)。然而,众所周知,标准的DFT公式(例如,广义梯度近似)不足以建模OV,需要更高的理论水平。嵌入式群集方法提供了一种有希望的方法,可以准确计算$ e_ \ textrm {ov} $,从而访问所有电子结构方法。这种方法的核心是构建位于合适的嵌入环境中的量子(机械处理)簇。不幸的是,当前构造量子簇的方法要么需要大型系统大小,防止应用高级方法或需要大量的手动输入,从而阻止对多个系统的研究。在这项工作中,我们提出了一种系统的和一般的量子群集设计方案,该方案可以确定小型收敛的量子簇,用于研究金属氧化物中的OV,并具有准确的方法,例如局部耦合群集,具有单,双扰动和扰动三重激发[CCSD(t)]。我们将此协议应用于金红石Tio2和Rocksalt Mgo的整体和表面平面上,并通过此方法生成了$ e_ \ textrm {ov} $的第一个准确且良好的确定。这些参考值用于基准在DFT中基准交换相关功能,我们发现所有研究的功能都低估了$ e_ \ textrm {ov} $,沿雅各布梯子的rungs的平均误差降低。该协议可自动用于高通量计算,可以推广以研究其他点缺陷或吸附物。

The O vacancy (Ov) formation energy, $E_\textrm{Ov}$, is an important property of a metal-oxide, governing its performance in applications such as fuel cells or heterogeneous catalysis. These defects are routinely studied with density functional theory (DFT). However, it is well-recognized that standard DFT formulations (e.g. the generalized gradient approximation) are insufficient for modeling the Ov, requiring higher levels of theory. The embedded cluster method offers a promising approach to compute $E_\textrm{Ov}$ accurately, giving access to all electronic structure methods. Central to this approach is the construction of quantum(-mechanically treated) clusters placed within suitable embedding environments. Unfortunately, current approaches to constructing the quantum clusters either require large system sizes, preventing application of high-level methods, or require significant manual input, preventing investigations of multiple systems simultaneously. In this work, we present a systematic and general quantum cluster design protocol that can determine small converged quantum clusters for studying the Ov in metal-oxides with accurate methods such as local coupled cluster with single, double and perturbative triple excitations [CCSD(T)]. We apply this protocol to study the Ov in the bulk and surface planes of rutile TiO2 and rocksalt MgO, producing the first accurate and well-converged determinations of $E_\textrm{Ov}$ with this method. These reference values are used to benchmark exchange-correlation functionals in DFT and we find that all studied functionals underestimate $E_\textrm{Ov}$, with the average error decreasing along the rungs of Jacob's ladder. This protocol is automatable for high-throughput calculations and can be generalized to study other point defects or adsorbates.

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