Stability and electronic properties of small boron nitride nanotubes

We report the stability and electronic structures of the boron nitride nanotubes (BNNTs) with diameters below 4 Å by semiempirical quantum mechanical molecular dynamics simulations and ab initio calculations. Among them (3,0), (3,1), (2,2), (4,0), (4,1), and (3,2) BNNTs can be stable well over room temperature. These small BNNTs become globally stable when encapsulated in a larger BNNT. It is found that the energy gaps and work functions of these small BNNTs are strongly dependent on their chirality and diameters. The small zigzag BNNTs become desirable semiconductors and have peculiar distribution of nearly free electron (NFE) states due to strong hybridization effect. When such a small BNNT is inserted in a larger one, the energy gap of the formed double-walled BNNT can be even much reduced due to the coupled effect of wall buckling difference and interwall NFE-π∗ hybridization.