论文标题

多层石墨烯的混合功能电子结构

Hybrid-functional electronic structure of multilayer graphene

论文作者

Campetella, Marco, Nguyen, Nguyen Minh, Baima, Jacopo, Maschio, Lorenzo, Mauri, Francesco, Calandra, Matteo

论文摘要

如使用半局部功能的密度功能理论计算所预测的,具有菱形和伯纳尔堆积的多层石墨烯被认为是金属的。但是,最近的角度分辨光发射和传输数据已经质疑了这一观点。特别是,建议菱形片是磁绝缘子。由偶数层组成的Bernal薄片是绝缘的,而由奇数层组成的片则是伪造的。在这里,通过系统地对平面波代码进行基准测试,我们为石墨烯多层开发了非常准确的全电子高斯基集。我们发现,与我们先前的计算一致,菱形堆叠的多层石墨烯被覆盖和磁性。但是,价带曲率和电子结构的细节取决于基础集。只有大大扩展的基集能够正确地重现K点的Valence频段顶部的有效质量,而流行的POB-TZVP基集将导致严重的高估。在Bernal堆叠的情况下,我们表明,精确的交换间隙由四层组成,并为n = 3、6、7、8的伪群打开。但是,间隙或伪群的大小及其作为厚度的行为与实验数据不兼容。此外,杂种功能导致5层的金属溶液和5、6和8层的磁接地状态。磁性非常弱,实际上对电子结构没有影响,并且磁矩主要集中在中央层中。我们对三层伯纳尔石墨烯多层的混合功能计算与非磁性GW计算非常吻合。对于较厚的多层,我们的计算是低能电子结构的许多体育理论建模的基准。

Multilayer graphene with rhombohedral and Bernal stacking are supposed to be metallic, as predicted by density functional theory calculations using semi-local functionals. However recent angular resolved photoemission and transport data have questioned this point of view. In particular, rhombohedral flakes are suggested to be magnetic insulators. Bernal flakes composed of an even number of layers are insulating, while those composed of an odd number of layers are pseudogapped. Here, by systematically benchmarking with plane waves codes, we develop very accurate all-electron Gaussian basis sets for graphene multilayers. We find that, in agreement with our previous calculations, rhombohedral stacked multilayer graphene are gapped for and magnetic. However, the valence band curvature and the details of the electronic structure depend crucially on the basis set. Only substantially extended basis sets are able to correctly reproduce the effective mass of the valence band top at the K point, while the popular POB-TZVP basis set leads to a severe overestimation. In the case of Bernal stacking, we show that exact exchange gaps the flakes composed by four layers and opens pseudogaps for N = 3, 6, 7, 8. However, the gap or pseudogap size and its behaviour as a function of thickness are not compatible with experimental data. Moreover, hybrid functionals lead to a metallic solution for 5 layers and a magnetic ground state for 5, 6 and 8 layers. Magnetism is very weak with practically no effect on the electronic structure and the magnetic moments are mostly concentrated in the central layers. Our hybrid functional calculations on trilayer Bernal graphene multilayers are in excellent agreement with non-magnetic GW calculations. For thicker multilayers, our calculations are a benchmark for manybody theoretical modeling of the low energy electronic structure.

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