Novel superhard tetragonal hybrid sp3/sp2 carbon allotropes Cx (x = 5, 6, 7): Crystal chemistry and ab initio studies

Novel superhard tetragonal carbon allotropes C5, C6, and C7, characterized by the presence of sp3- and sp2-like carbon sites, have been predicted from crystal chemistry and extensively studied by quantum density functional theory (DFT) calculations. All new allotropes were found to be cohesive, with crystal densities and cohesive energies decreasing along the C5 C6 C7 series due to the greater openness of the structures resulting from the presence of C=C ethene and C=C=C propadiene subunits, and mechanically stable with positive sets of elastic constants. The Vickers hardness evaluated by different models qualifies all allotropes as superhard. Phonon band structures confirm that the new allotropes are also dynamically stable. The electronic band structures reveal their metallic-like behavior due to the presence of sp2-hybridized carbon.