The excited state dynamics of an unnatural base pair (UBP) d5SICS/dNaM were investigated by accurate ab-initio calculations. Time-dependent density functional and high-level multireference calculations (MS-CASPT2) were performed to elucidate the excitation of this UBP and its excited state relaxation mechanism. After excitation to the bright state S2 (ππ*), it decays to the S1 state and then undergoes efficient intersystem crossing to the triplet manifold. The presence of sulfur atom in d5SICS leads to strong spin-orbit coupling (SOC) and a small energy gap that facilitates intersystem crossing from S1 (ns π*) to T2 (ππ*) followed by internal conversion to T1 state. Similarly in dNaM, the deactivation pathway follows analogous trends. CASPT2 calculations suggest that the S1 (ππ*) state is a dark state below the accessible S2 (ππ*) bright state. During the ultrafast deactivation, it exhibits bond length inversion. From S1 state, significant SOC leads the population transfer to T3 due to a smaller energy gap. Henceforth, fast internal conversion occurs from T3 to T2 followed by T1 . From time-dependent trajectory surface hopping dynamics, it is found that excited state relaxation occurs on a sub-picosecond timescale in d5SICS and dNaM. Our findings strongly suggest that there is enough energy available in triplet state of UBP to generate reactive oxygen species and induce phototoxicity with respect to cellular DNA.
Keywords: DNA-light interactions; excited state dynamics; spin-orbit couplings.; surface hopping trajectories; synthetic biology; unnatural DNA bases.
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