Stony Brook University graduate student Qiang Zhu, together with Professor of Geosciences and Physics, Artem R. Oganov, postdoc Andriy O. Lyakhov and their colleagues from the University de Oviedo in Spain, have predicted three new forms of carbon, the findings of which were published in a paper entitled “Denser than diamond: Ab initio search for superdense carbon allotropes,” in the June 7, 2011 online edition of Physical Review B. So far, each new found modification of carbon resulted in a scientific, technological revolution – the same could happen now, if scientists can find a way to synthesize these new forms of carbon.
Elemental carbon possesses a unique range of structures and properties – from ultrsoft graphite to superhard diamond, and also including elusive carbines, beautifully symmetric fullerenes, carbon nanotubes, and the recently established new form, M-carbon (the structure of which was predicted by Oganov in 2006). Properties of all these modifications of carbon are so interesting and so tunable that two Nobel prizes were awarded recently for their studies (the 1996 Chemistry and 2010 Physics awards).
Graphene is the densest two-dimensional material, with unique mechanical and electronic properties and having some electrons moving with near-light velocities and behaving as if they had zero mass. Diamond has set several records – it is not only the hardest known material, but also has denser packing of atoms than any other known three-dimensional material. When doped by boron, diamond displays superconductivity and is the only know materials simultaneously displaying superhardness and superconductivity.
Now Zhu, Oganov, and their colleagues propose three new structures of carbon, which should be more than 3% denser than diamond. Greater density means that electrons should have a higher kinetic energy (that is, move faster). Calculations of Zhu et al. show that the new modifications are almost as hard as diamond, but do not exceed its hardness. Their electronic properties are very diverse, with the band gap ranging from 3.0 eV to 7.3 eV. Band gap is the minimum separation in energy between occupied and unoccupied electronic orbitals and is the most important characteristic of the electronic structure of materials. Such a wide range of band gaps implies the possibility of tuning the electronic properties. The band gap of 7.3 eV predicted for the tP12 modification is the largest value for all forms of carbon.
Other interesting properties include ultralow compressibility – when subjected to pressure, the new forms of carbon will contract less than most materials (even slightly less than diamond, the current record holder). They have higher refractive indices and stronger light dispersion than diamond – which means better brilliance and color effects than those displayed by diamond. “Carbon is an inexhaustible element in its chemical diversity and in the multitude of its physical applications”, says Professor Oganov. “If these predicted forms of carbon can be synthesized, they may find important technological roles”. Researchers believe that the new forms of carbon, thanks to their high densities, could be synthesized by shock compression of low-density modifications, or by directed growth on substrate.
Figure caption: Crystal structure of one of the superdense forms of carbon predicted by Zhu et al.
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