A dispersion‐corrected density functional theory study of the noncovalent interactions between nucleobases and carbon nanotube models containing stone–wales defects

The noncovalent bonding between nucleobases (NBs) and Stone–Wales (SW) defect‐containing closed‐end single‐walled carbon nanotubes (SWNTs) was theoretically studied in the framework of density function theory using a dispersion‐corrected functional PBE‐G06/DNP. The models employed in this study were armchair nanotube (ANT) (5,5) and zigzag nanotube (ZNT) (10,0), which incorporated SW defects in different orientations. In one of them, the (7,7) junction is tilted with respect to SWNT axis (ANT‐t and ZNT‐t), whereas in ANT‐p and ZNT‐p models the (7,7) junction is parallel and perpendicular to the axis, respectively. The binding energies for uracil, thymine, cytosine, 5‐methylcytosine, adenine, and guanine interacting with the defect‐containing nanotube models were compared to the values previously obtained with the same calculation technique for the case of defect‐free SWNTs, both in the gas phase (vacuum) and in aqueous medium. For most models, the interaction strength tends to be higher for purine than for pyrimidine complexes, with a clear exception of the systems including ZNT‐p, both in vacuum and in aqueous medium. As it could be expected, the binding strength in the latter case is lower as compared to that in vacuum, roughly by 2–4 kcal/mol, due to the implicit inclusion of a medium (i.e., water) via the conductor‐like screening model model. The closest contacts between NBs and SWNT models, frontier orbital distribution, and highest‐occupied molecular orbital–lowest‐unoccupied molecular orbital gap energies are analyzed as well. © 2019 Wiley Periodicals, Inc. The interaction strength tends to be higher sensitive not only to the chirality (armchair or zigzag), but also to the orientation of Stone–Wales defect (tilted or parallel/perpendicular to the nanotube axis). In the case of complexes with both ZNT‐t and ZNT‐p, nucleobases adsorption on SW‐defective sites is always considerably weaker than on ideal nanotube sidewalls.