Triplet-State Formation along the Ultrafast Decay of Excited Singlet Cytosine

We address the possibility of populating the lowest triplet state of cytosine by an "intrinsic"mechanism, namely, intersystem crossing (ISC) along the ultrafast internal conversion pathway of the electronically excited singlet species. For this purpose, we present a discussion of the ISC process and triplet-state reactivity based on theoretical analysis of the spin-orbit strength and the potential energy surfaces for the relevant singlet and triplet states of cytosine. High-level ab initio computations show that ISC is possible in wide regions of the singlet manifold along the reaction coordinate that controls the ultrafast internal conversion to the ground state. Thus, the ISC mechanism documented here provides a possibility to access the triplet state, which has a key role in the photochemistry of the nucleic acid bases.