Evolution of the Excitonic State of DNA Stacked Thymines: Intrabase ππ* → S 0 Decay Paths Account for Ultrafast (Subpicosecond) and Longer (>100 ps) Deactivations

Monomer-like ring puckering decay paths for two stacked quantum mechanical thymines inside a solvated DNA duplex described at the molecular mechanics level are mapped using a hybrid CASPT2//CASSCF/MM protocol that accounts for steric, electronic and electrostatic interactions within the nucleobases native environment. Asymmetric stacking between nucleobases open ups different intrabase ππ* decay paths accounting for distinctive excited state lifetimes, spanning the subps to subns time window.