Structural changes of Li2C2 under pressure were studied by synchrotron x-ray diffraction in a diamond anvil cell under hydrostatic conditions and by using evolutionary search methodology for crystal structure prediction. We show that the high-pressure polymorph of Li2C2, which forms from the Immm ground-state structure (Z = 2) at around 15 GPa, adopts an orthorhombic Pnma structure with Z = 4. Acetylide C-2 dumbbells characteristic of Immm Li2C2 are retained in Pnma Li2C2. The structure of Pnma Li2C2 relates closely to the anticotunnite-type structure. C-2 dumbbell units are coordinated by nine Li atoms, as compared to eight in the antifluorite structure of Immm Li2C2. First-principles calculations predict a transition of Pnma Li2C2 at 32 GPa to a topologically identical phase with a higher Cmcm symmetry. The coordination of C-2 dumbbell units by Li atoms is increased to 11. The structure of Cmcm Li2C2 relates closely to the Ni-2 In-type structure. It is calculated that Cmcm Li2C2 becomes metallic at pressures above 40 GPa. In experiments, however, Pnma Li2C2 is susceptible to irreversible amorphization.
|Number of pages||8|
|Journal||Physical review B: Condensed matter and materials physics|
|Publication status||Published - 19 Aug 2015|
- CRYSTAL-STRUCTURE PREDICTION
- BRILLOUIN-ZONE INTEGRATIONS
- AUGMENTED-WAVE METHOD
- CALCIUM CARBIDES