Dominant Role of Quantum Anharmonicity in the Stability and Optical Properties of Infinite Linear Acetylenic Carbon Chains

Carbyne, an infinite-length straight chain of carbon atoms, is supposed to undergo a second order phase transition from the metallic bond-symmetric cumulene (═C═C═) ∞ oward the distorted insulating polyyne chain (-C≡C-) ∞ displaying bond-length alternation. However, recent synthesis of ultra long carbon chains (∼6000 atoms, [Nat. Mater., 2016 , 15 , 634]) did not show any phase transition and detected only the polyyne phase, in agreement with previous experiments on capped finite carbon chains. Here, by performing first-principles calculations, we show that quantum-anharmonicity reduces the energy gain of the polyyne phase with respect to the cumulene one by 71%. The magnitude of the bond-length alternation increases by increasing temperature, in stark contrast with a second order phase transition, confining the cumulene-to-polyyne transition to extremely high and unphysical temperatures. Finally, we predict that a high temperature insulator-to-metal transition occurs in the polyyne phase confined in insulating nanotubes with sufficiently large dielectric constant due to a giant quantum-anharmonic bandgap renormalization.