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Very recently, half-hydrogenated germanene has been achieved in an experiment. In this paper, we investigate the effects of tetracyanoquinodimethane (TCNQ) molecular adsorption and strain on the electronic properties of half-hydrogenated germanene through first-principles. As an electron-acceptor molecule, TCNQ is exploited to non-covalently functionalize the half-hydrogenated germanene. However, this physical adsorption induces a ferromagnetic semiconductor–metal transition in half-hydrogenated germanene due to charge transfer from the substrate to the TCNQ molecule. More importantly, the superstructure of half-hydrogenated germanene/TCNQ is extremely sensitive to biaxial tensile strain. Under the biaxial tensile strain of 0.25%, the ferromagnetic semiconductor–metal transition induced by molecular adsorption can surprisingly be overturned. Meanwhile, a strong p-type doping is exhibited. Remarkably, it would return from a ferromagnetic semiconductor to a metal again when the biaxial tensile strain increases to 1.5%. Our analysis based on the structural and electronic properties of half-hydrogenated germanene/TCNQ indicates that such metal–semiconductor–metal transition in half-hydrogenated germanene/TCNQ under biaxial tensile strain may originate from the strong local deformation, resulting in the energy of the valence band maximum decreasing below or increasing above the Fermi level. [ABSTRACT FROM AUTHOR]

The O2 dissociation and O atoms adsorption on free-standing germanene are studied by using first-principles calculations in this paper. Compared with the extremely active silicene in oxygen atmosphere, germanene is found to be less active due to an energy barrier for dissociation of about 0.57 eV. Moreover, the dissociated oxygen atom follows two opposite migration pathways on the germanene surface, which is quite different from the case of silicene. Furthermore, the migration and desorption of O atoms at room temperature are relatively difficult due to the strong Ge-O bonding, resulting in the formation of germanium oxides. Our results reveal the interplay between germanene and O2 and suggest the enhanced stability of germanene in oxygen atmosphere compared with silicene. [ABSTRACT FROM AUTHOR]

Recently, Yoo and Zhou [ACS Nano 5, 3020-3026 (2011)] reported that graphene can be directly used as electrode for Li-air batteries, suggesting that graphene itself can be served as catalyst for O2 dissociation reaction. In this work, we show from density functional theory calculations that the O2 dissociation reaction energy barrier is substantially decreased on the graphene surface comparing to that of in vacuum. Furthermore, N-doping can further decrease the energy barrier from 2.39 eV (undoped case) to 1.20 eV. The O2 molecule physical adsorption, O atom chemical adsorption at the graphene, and N-doped graphene surfaces are also simulated. [ABSTRACT FROM AUTHOR]

The lithium ion dynamics in graphite, an important anode material for lithium ion batteries, is strongly related with the layer-to-layer distance (d-spacing) and the stacking modes of graphite. We studied these relationships by first-principles calculations. It is found that a larger d-spacing results in the easier transformation of the stacking mode from A-B stacking to A-A stacking when lithium atoms are inserted. This transformation is unfavorable to the lithium diffusion because of the larger diffusion energy barrier for lithium in A-A stacking graphite compared to that in A-B one. On the other hand, as the d-spacing increases, the diffusion energy barrier for lithium in A-A stacking graphite decreases substantially, thus being favorable to the lithium diffusion. These results give a better understanding of the lithium ion dynamics in graphite, and show that it is possible to optimize the lithium ion dynamics in graphite by properly adjusting the d-spacing. [ABSTRACT FROM AUTHOR]

Structural and electronic properties of the λ-MnO2(001) surface are investigated applying density functional theory approach. The calculations show that all Mn ions at unreconstructed smooth surface preserve the +4 oxidation state observed in the bulk. Upon the λ-MnO2(001) reconstruction, one fourth of Mn ions at the surface undergo a change of the oxidation state from +4 to +3, although the reconstruction does not change the Mn coordination number with oxygen. This is accompanied with the filling of initially empty 3dz2 states localized on cations with one electron denoted by two neighboring O atoms. Although the reconstruction leads to an energy gain of 0.04 eV per surface unit cell, it is not a spontaneous process since it proceeds with an activation energy of 0.12 eV. [ABSTRACT FROM AUTHOR]