From PAH to fullerenes: Closing a nano bowl with a nano lid
Quantum chemical DLPNO-CCSD(T)/cc-pVDZ//B3LYP/6–31G(d) calculations have been performed to unravel the formation mechanism of buckminsterfullerene (C 60 ) via the reaction of the C 40 nano bowl (C 40 H 10 ) and corannulene (C 20 H 10 ). The generated potential energy surfaces and molecular properties were further utilized to evaluate equilibrium constants and rate constants of elementary chemical reactions involved in the C 60 synthesis. The overall C 40 H 10 + C 20 H 10 → C 60 + 10H 2 reaction is shown to be highly exoergic and hence thermodynamically favorable at temperatures above 700 K and a kinetically feasible pathway under high-temperature conditions was revealed. This route involves hydrogen atom abstraction steps to activate closed-shell reactants/intermediates alternating with cyclodehydrogenation reactions eventually zipping the edges between the reacting C 40 and C 20 units by consecutive closures of six- and five-membered rings between them. The reaction is driven/catalyzed by hydrogen atoms which carry out the hydrogen abstractions from C 60 H x and are later recovered on the cyclodehydrogenation stages. The initial association reaction, C 40 H 9 + C 20 H 10 → C 60 H 18 + H, linking the two units by a covalent C-C bond appears to represent the kinetic bottleneck of the whole multistep process. This reaction is fast at low temperatures but slows down and has its equilibrium shifted toward the reactants at high temperatures. Here, the feasibility of the proposed mechanism corroborates the hypothesis that C 60 can be produced through a series of elementary reactions typical for the PAH growth.