Ultraviolet Photodissociation Spectroscopy of [dAMP–H] ⁻ at Low Temperature

Nucleotide fragmentation after photoexcitation in the ultraviolet is a potential cause for damage to DNA strands. Consequently, the fragmentation process needs to be explored to understand the stability of nucleotides on a molecular level. Here, we present wavelength-dependent relative photoabsorption cross section measurements of [dAMP-H]^- below the photodetachment threshold, which lead to fragmentation along several different channels. Several spectral features are observed in the broad absorption peak in the range of 240 to 270 nm, the resolution of which we attribute to the low temperature of 3 K achieved in our cryogenic 16-pole radiofrequency wire trap. These features likely originate from different Franck-Condon-active vibrational bands in only one or two different conformers. Quantum chemical calculations predict that the spectrum originates from a strong ππ* excitation located at the adenine moiety. Furthermore, the wavelength-dependent yield of the five observed photofragments was studied. This revealed no preferred single photofragment, but showed different trends for different fragments as a function of photon energy. Finally, an absolute photofragmentation cross section of [dAMP-H]^- was obtained by comparison with the photodetachment cross section of I^-.