Narváez Wilmer Esteban Vallejo, Rodríguez Luis Daniel Solís, de la Garza Cesar Gabriel Vera, Fomina Lioudmila, Fomine Serguei
Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Apartado Postal 70-360, CU, Coyoacán, 04510, Mexico, DF, Mexico.
J Mol Model. 2020 Jul 10;26(8):204. doi: 10.1007/s00894-020-04463-9.
The electronic structure of the van der Waals heterostructures (HSs) of the phosphorene (P) nanoflakes (NFs) with graphene (G) and its allotropy (H1 and H2) NFs, and their complexes with Li have been studied using dispersion-corrected TPSS functional. According to the calculations, the attractive interactions in HSs come from dispersion. It has a relatively small contribution to the binding energy in Li complexes, especially for these forming complexes with G, H1, or H2 NF side. The binding energies between the individual NFs and Li atoms increase in the order G < H1 = H2 = P. The formation of HSs results in a synergetic effect for Li binding energies. This effect is the most notable for phosphorene binding sites; however, it also holds for G, H1, and H2 NFs. The formation of complexes with Li always leads to the almost complete charge transfer from Li to the NFs or HSs. In the case of HSs, the unpaired electron of Li is always located at the carbon NF side independently on the Li binding location. The activation energies of Li hopping for individual NFs are notably higher for P comparing with G, H1, or H2 NFs. The formation of HSs rises slightly the activation energies of Li hopping due to the increase of binding energies in Li-HS complexes. Graphical abstract.
采用色散校正的TPSS泛函研究了磷烯（P）纳米片（NFs）与石墨烯（G）及其同素异形体（H1和H2）NFs的范德华异质结构（HSs）的电子结构，以及它们与锂的复合物。根据计算，HSs中的吸引相互作用来自色散。它对锂复合物的结合能贡献相对较小，特别是对于那些与G、H1或H2 NF面形成复合物的情况。单个NFs与锂原子之间的结合能按G＜H1 = H2 = P的顺序增加。HSs的形成对锂结合能产生协同效应。这种效应在磷烯结合位点最为显著；然而，对于G、H1和H2 NFs也成立。与锂形成复合物总是导致锂几乎完全向NFs或HSs发生电荷转移。对于HSs，锂的未成对电子总是独立于锂的结合位置位于碳NF面。与G、H1或H2 NFs相比，磷烯单个NFs的锂跳跃活化能明显更高。由于Li-HS复合物结合能的增加，HSs的形成使锂跳跃活化能略有升高。图形摘要。
