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| - Dehydrogenation and Other Non-radiative Relaxation Processes in Gas-Phase Metal−DNABase Complexes
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| - Photoinduced dehydrogenations of gas-phase Al−guanine, Mn−guanine, and the Al-base pair adduct Al−guanine−cytosine have been observed. Upper and lower limits on the minimum photon energy required toeffect the dehydrogenation have been determined for these species. Species were generated using a laserablation source and were detected with laser photoionization/time-of-flight mass spectrometry. Only metalatedspecies were observed to dehydrogenate, and the effect of metal on the photochemistry of guanine and cytosinehas been investigated using density functional theory (DFT). Avoided crossings between the ground and firstelectronically excited states are features specific to the metalated species and are likely responsible for themetal-specific dehydrogenation observed. The rapid nonradiative relaxation believed to manifest thedehydrogenation is consistent with the dominance of multiphoton contributions to the mass spectral signalsobserved which also stems from rapid nonradiative relaxation. In this context, the photophysics of the gas-phase complexes is similar to that of solution-phase bases where nonradiative relaxation processes alsodominate.
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