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The random phase approximation applied to solids, molecules, and graphene-metal interfaces: From weak to strong binding regimes

机译:随机相位近似应用于固体,分子和   石墨烯 - 金属界面:从弱到强的结合方式

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摘要

The random phase approximation (RPA) is attracting renewed interest as auniversal and accurate method for first-principles total energy calculations.The RPA naturally accounts for long-range dispersive forces withoutcompromising accuracy for short range interactions making the RPA superior tosemi-local and hybrid functionals in systems dominated by weak van der Waals ormixed covalent-dispersive interactions. In this work we present planewave-based RPA calculations for a broad collection of systems with bond typesranging from strong covalent to van der Waals. Our main result is the RPApotential energy surfaces of graphene on the Cu(111), Ni(111), Co(0001),Pd(111), Pt(111), Ag(111), Au(111), and Al(111) metal surfaces, which representarchetypical examples of metal-organic interfaces. Comparison with semi-localdensity approximations and a non-local van der Waals functional show that onlythe RPA captures both the weak covalent and dispersive forces which are equallyimportant for these systems. We benchmark our implementation in the GPAWelectronic structure code by calculating cohesive energies of graphite and arange of covalently bonded solids and molecules as well as the dissociationcurves of H2 and H2+. These results show that RPA with orbitals from the localdensity approximation suffers from delocalization errors and systematicallyunderestimates covalent bond energies yielding similar or lower accuracy thanthe Perdew-Burke-Ernzerhof (PBE) functional for molecules and solids,respectively.
机译:随机相位逼近(RPA)作为一种通用且准确的第一原理总能量计算方法吸引了新的兴趣.RPA自然地考虑了远程分散力而不会影响短距离相互作用的准确性,从而使RPA优于半局部和混合功能在弱范德华或混合的共价-分散相互作用占主导的系统中。在这项工作中,我们提出了基于平面波的RPA计算,适用于键类型范围从强共价到范德华斯的各种系统。我们的主要结果是石墨烯在Cu(111),Ni(111),Co(0001),Pd(111),Pt(111),Ag(111),Au(111)和Al( 111)金属表面,代表金属-有机界面的典型示例。与半局部密度近似和非局部范德华函数的比较表明,只有RPA捕获了对于这些系统同样重要的弱共价力和分散力。我们通过计算石墨的内聚能以及一系列共价键合的固体和分子以及H2和H2 +的解离曲线,在GPAW电子结构代码中对实现进行基准测试。这些结果表明,具有局部密度近似轨道的RPA受到离域误差的影响,并且系统地低估了共价键能,其准确度与分子和固体的Perdew-Burke-Ernzerhof(PBE)分别相似或更低。

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