Selective Interaction of Large or Charge-Transfer Aromatic Molecules with Metallic Single-Wall Carbon Nanotubes: Critical Role of the Molecular Size and Orientation

Using first principles calculations, we report for the first time that large nearly neutral aromatic molecules, such as naphthalene and anthracene, and small charge-transfer aromatic molecules, such as TCNQ and DDQ, interact more strongly with metallic single-wall carbon nanotubes (SWNTs) versus their semiconducting counterparts as the molecular orientation of DDQ is taken into account. Hence two new mechanisms for separating metallic and semiconducting SWNTs via noncovalent π−π stacking or charge-transfer interaction are suggested.