First-principle study of structure and stability of nickel carbides.

Computational studies of nickel carbides, particularly Ni(2)C, are scarce. A systematic density functional theory study is reported for Ni(2)C, along with NiC and Ni(3)C, to understand the stability and electronic structure of nickel carbides of varying stoichiometry. A comprehensive study was executed that involved 28 trial structures of varying space group symmetry for Ni(2)C. An analysis of the electronic structure, geometry and thermodynamics of Ni(2)C is performed, and compared with that for Ni(3)C and NiC as well as several defect structures of varying composition. It is found that the most stable ground state arrangement of Ni(2)C exists within a simple orthorhombic lattice and that it has metallic character. The calculated formation energies (kcal mol(-1)) of NiC, Ni(2)C, and Ni(3)C are 48.6, 7.9 and 6.4, respectively.