Biradical radiationless decay channel in adenine and its derivatives

Coupled-cluster calculations of increasing accuracy (approximate doubles: CC2; doubles: EOM-CCSD; connected triples: CR-EOM-CCSD(T)) for CIS-optimized potential energy profiles of adenine and its derivatives indicate that the ultrafast internal conversion of the optically excited π π* state occurs through a state switch to a biradical state, which intersects the ground state at a lower energy. The electronic nature of the biradical state is defined by an electronic configuration in which one unpaired electron occupies a π* orbital confined to the five-membered ring. The second unpaired electron is localized very strongly on a p-type C2 atomic orbital of the six-membered ring. The biradical state minimum has a strongly puckered six-membered ring and a C2–H bond, which is twisted nearly perpendicular to the average ring plane. Consistent with the biradical-mediated internal conversion, the π π* state lifetime is extremely short in adenine and 9-methyladenine, which have barrierless crossing to the biradical...

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