Singlet-Triplet States Interaction Regions in DNA/RNA Nucleobase Hypersurfaces

The present study provides new insight into the intrinsic mechanisms for the population of the triplet manifold in DNA nucleobases by determining, at the multiconfigurational CASSCF/CASPT2 level, the singlet-triplet states crossing regions and the main decay paths for their lowest singlet and triplet states after near-UV irradiation. The studied singlet triplet interacting regions are accessible along the minimum energy path of the initially populated singlet bright (1)pi pi* state. In particular, all five natural DNA/RNA nucleobases have, at the end of the main minimum energy path and near a conical intersection of the ground and (1)pi pi* states, a low-energy, easily accessible, singlet-triplet crossing region directly connecting the lowest singlet and triplet pi pi* excited states. Adenine, thymine, and uracil display additional higher-energy crossing regions related to the presence of low-lying singlet and a triplet n pi* state. These funnels are absent in guanine and cytosine, which have the bright (1)pi pi* state lower in energy and less accessible n pi* states. Knowledge of the location and accessibility of these regions, in which the singlet-triplet interaction is related to large spin-orbit coupling elements, may help to understand experimental evidence such as the wavelength dependence measured for the triplet formation quantum yield in nucleobases and the prevalence of adenine and thymine components in the phosphorescence spectra of DNA.