Cyclobutane thymine dimerization is the most prominent DNA photoinduced damage. While the ultrafast mechanism that proceeds in the singlet manifold is nowadays well established, the triplet-state pathway is not completely understood. Here we report the underlying mechanism of the photosensitized dimerization process in the triplet state. Quantum chemical calculations, combined with wavefunction analysis, and nonadiabatic molecular dynamics simulations demonstrate that this is a stepwise reaction, traversing a long-lived triplet biradical intermediate, which is characterized as a Frenkel exciton with very small charge-transfer character. The low yield of the reaction is regulated by two factors: (i) a relatively large energy barrier that needs to be overcome to form the exciton intermediate, and (ii) a bifurcation of the groundstate potential-energy surface that mostly leads back to the Franck-Condon region because dimerization requires a very restricted combination of coordinates and velocities at the event of non-radiative decay to the ground state.
Graphical abstract
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.