Prediction of the [4 + 2]- and [5 + 4]-cycloaddition reactions in zig-zag carbon nanotubes via an ambimodal transition state: density functional theory calculations.

A unique type of chemical reaction known as an ambimodal reaction has drawn tremendous attention owing to its intriguing feature of forming multiple (two or more) products from the same (single) transition state. In contrast to conventional reactions, bifurcation of the potential energy surface takes place in ambimodal reactions. Density functional theory (DFT) based calculations were performed to probe the Diels-Alder (DA) cycloaddition reactions of various carbon nanotubes (CNTs) with 1,3-butadiene. The present investigation reveals the possibility of ambimodal transition state formation on a potential energy surface (PES) corresponding to an unusual [5 + 4]-cycloadduct along with the conventional [4 + 2]-cycloadduct. The ground state of the [5 + 4]-cycloadduct obtained from butadiene and the H-terminated CNTs is a triplet ( 3 T) state, but on the other hand the [4 + 2]-cycloadduct is a singlet ( 1 S) state. The [5 + 4]-adduct is energetically more stable in comparison with the [4 + 2]-adduct. The possibility of the formation of the [5 + 4]-adduct is validated using frontier molecular orbitals. The length of the nanotube significantly influences the overall kinetics and thermodynamics of the reaction.