First-Principles Study of Chemisorption of Oxygen and Aziridine on Graphitic Nanostructures

Using ab initio plane wave pseudopotential calculations, we study the energetics and structure of adsorbed linear arrays of oxygen and aziridine on carbon nanotubes, graphitic ribbons, and graphene sheets. Chemisorption of arrays of O or NH causes splitting of the CC bond and local deformation of the graphitic structures. The (3,3) nanotube cross section assumes a teardrop-like shape, while graphene sheets warp into a new local geometry around the chemisorbed molecules. The interior of a (3,3) nanotube is less prone to oxidation than the exterior because of steric effects. A zigzag (6,0) nanotube is less reactive and thus chemically more stable than an armchair (3,3) nanotube. The results suggest a partial explanation for the experimentally observed selective etching of metallic carbon nanotubes

Gas−Surface Chemical Reactions at High Collision Energies?

Most gas−surface chemical reactions occur via reaction of adsorbed species to form a thermal-energy (kT) product; however, some instances exist where an energetic projectile directly reacts with an adsorbate in a single-collision event to form a hyperthermal product (with a kinetic energy of a few eV). Here we show for the first time that 30−300 eV F^+ bombardment of fluorinated Ag and Si surfaces produces “ultrafast” F_2^− products with exit energies of up to 90 eV via a multistep direct-reaction mechanism. Experiments conclusively show that the projectile F atom ends up in the fast molecular product despite the fact that the impact energy is far greater than typical bond energies

Dirac Cones and Nodal Line in Borophene

Two-dimensional single-layer boron (borophene) has emerged as a new material with several intriguing properties. Recently, the β₁₂ polymorph of borophene was grown on Ag(111), and observed to host Dirac fermions. Similar to graphene, β₁₂ borophene can be described as atom-vacancy pseudoalloy on a closed-packed triangular lattice; however, unlike graphene, the origin of its Dirac fermions  is yet unclear. Here, using first-principles calculations, we probe the origin of Dirac fermions in freestanding and Ag(111)-supported β₁₂ borophene. The freestanding β₁₂ sheet hosts two Dirac cones and a topologically nontrivial Dirac nodal line with interesting Dirac-like edge states. On Ag(111), the Dirac cones develop a gap, whereas the topologically protected nodal line remains intact, and its position in the Brillouin zone matches that of the Dirac-like electronic states seen in the experiment. The presence of nontrivial topological states near the Fermi level in borophene makes its electronic properties important for both fundamental and applied research

Can Two-Dimensional Boron Superconduct?

Two-dimensional boron is expected to exhibit various structural polymorphs, all being metallic. Additionally, its small atomic mass suggests strong electron–phonon coupling, which in turn can enable superconducting behavior. Here we perform first-principles analysis of electronic structure, phonon spectra, and electron–phonon coupling of selected 2D boron polymorphs and show that the most stable structures predicted to feasibly form on a metal substrate should also exhibit intrinsic phonon-mediated superconductivity, with estimated critical temperature in the range of <i>T</i>_c ≈ 10–20 K