Original mechanism of transformation from soft metallic (sp2/sp3) C12 to ultra-dense and ultra-hard (sp3) semi-conducting C12: Crystal chemistry and DFT characterizations

Abstract

An original mechanism is proposed for a pressure-induced transformation of orthorhombic C12 from ground state normal pressure (NP) sp2/sp3 allotrope to ultra-dense and ultra-hard HP sp3 form. Upon volume decrease, the trigonal C=C parallel segments characterizing glitter-like tfi topology of NP C12 change to crossing C-C segments with the loss of sp2 character accompanied by a large densification with density=3.64 g/cm3, larger than diamond, defining a novel orthorhombic HP C12 with 44T39 topology. The crystal chemistry engineering backed with quantum density functional theory DFT-based calculations let determine the ground state structures and energy derived physical properties. Furthering on that, the E(V) equations of states (EOS) let define the equilibrium NP(E0,V0) allotrope at lower energy and higher volume versus HP(E0, V0) allotrope at higher energy and smaller volume. A potential pressure induced transformation NP to HP was estimated at ~100 GPa, reachable with a diamond anvil cell DAC. Both allotropes were found cohesive and mechanically stable with low and large Vickers hardness magnitudes: HV(tfi C12) =24 GPa and HV(44T39 C12) =90 GPa; the latter being close to diamond hardness (HV ~95 GPa). Besides, both allotropes were found dynamically stable with positive phonon frequencies and a spectroscopic signature of C=C high frequency bands in tfi C12. The electronic band structures show metallic behavior for NP tfi C12 and a small band gap for HP 44T39 C12 letting assign semiconducting properties. The work is meant to open further the scope of C(sp2)and C(sp3) transformation mechanisms that are fundamental in solid state physics and chemistry.