Grapheayne: a class of low-energy carbon allotropes with diverse optoelectronic and topological properties

Abstract: A series of carbon allotropes with novel optoelectronic and rich topological properties is predicted by systematic first-principles calculations. These fascinating carbon allotropes can be derived by inserting acetylenic linkages (-C$\equiv$C-) into graphite, hence they are termed as grapheaynes. Grapheaynes possess two different space groups, $P$2/$m$ or $C$2/$m$, and contain simultaneously the $sp$, $sp^2$, and $sp^3$ chemical bonds. They have formation energies lower than the already experimentally synthesized graphdiyne and other theoretically predicted carbon allotropes with acetylenic linkages. Particularly, when the width $n$ of grapheayne-$n$ exceeds 15, its cohesive energy is lower than that of diamond, and approaches that of graphite with increasing $n$. Remarkably, we find that some grapheaynes behave as semiconductors with direct narrow band gaps and own the highest absorption coefficients among all known semiconducting carbon allotropes, while some others are topological semimetals with nodal lines. Especially, some grapheaynes can be engineered with tunable direct band gaps in the range of 1.07-1.87 eV and have ideal properties for photovoltaic applications. Our work not only uncovers the unique atomic arrangement and prominent properties of the grapheayne family, but also offers a treasury that provides promising materials for catalyst, energy storage, molecular sieves, solar cell, and electronic devices.