Why alkali metals preferably bind on structural defects of carbon nanotubes: a theoretical study by first principles.

By using ab initio calculations we investigated the interaction of alkali metal atoms and alkali metal cations with perfect and defective carbon nanotubes. Our results show that the alkali metals prefer to interact with the pentagons and heptagons that appear on the defective site of the carbon nanotube rather than with the hexagons. The alkali metals remain always positively charged not depending on their charge state (neutral, cation) or the different carbon ring that they interact with. The molecular orbital energy level splitting from a defect creation on the carbon nanotube along with the localization of charge-electron density on the defect, results in binding the alkali metals more efficient. More interestingly, metallic sodium appears to bind very weak on the nanotube compared to the rest of alkali metals. The Na anomaly is attributed to the fact that unlike the K case, sodium's inner p shell falls energetically lower than carbon nanotube's p molecular orbitals. As a result, the Na p shell is practically excluded from any binding energy contribution. In the alkali metal cation case the electronegativity trend is followed.