Investigation of out-of-plane ordered Ti4MoSiB2 from first principles

The laminated ternary boride Mo 5 SiB 2 of T2 structure have two symmetrically inequivalent metallic sites, 16l and 4c, being occupied in a 4:1 ratio. The phase was recently shown to be stable for 80% substitution of Mo for Ti, at the majority site, forming an out-of-plane chemically ordered quaternary boride: Ti 4 MoSiB 2 . Considering that the hypothetical Ti 5 SiB 2 is theoretically predicted as not stable, a key difference in bonding characteristics is indicated for full substitution of Mo for Ti at the metallic sites. To explore the origin of formation of Ti 4 MoSiB 2 , we here investigate the electronic properties and bonding characteristics of Mo 5 SiB 2 , Ti 4 MoSiB 2 and Ti 5 SiB 2 through their density of states, projected crystal orbital Hamilton population (pCOHP), Bader charge partitioning and second order force constants. The bond between the two different metallic sites is found to be key to the stability of the compounds, evident from the pCOHP of this bond showing a peak of bonding states close to the Fermi level, which is completely filled in Mo 5 SiB 2 and Ti 4 MoSiB 2 , while only partially filled in Ti 5 SiB 2 . Furthermore, the lower electronegativity of Ti compared to Mo results in charge accumulation at the Si and B sites, which coincides with a reduced bond strength in Ti 5 SiB 2 compared to Mo 5 SiB 2 and Ti 4 MoSiB 2 . Bandstructure calculations show that all three structures are metallic. The calculated mechanical and elastic properties show reduced bulk ( B ) and elastic ( E ) moduli when introducing Ti in Mo 5 SiB 2 , from 279 and 365 GPa to 176 and 258 GPa, respectively. The Pugh criteria indicates also a slight reduction in ductility, with a G / B ratio increasing from 0.51 to 0.59.