Photoexcitation of Adenosine 5'-Triphosphate Anions in Vacuo: Probing the Influence of Charge State on the UV Photophysics of Adenine.

We report the first UV laser photodissociation spectra (4.0-5.8 eV) of gas-phase deprotonated adenosine 5'-triphosphate, diphosphate and monophosphate anions. The photodepletion spectra of these anions display strong absorption bands across the region of 4.6-5.2 eV, consistent with excitation of a primarily adenine-centered π-π* transition. The spectra appear insensitive to the charge of the species (i.e., the spectrum of [ATP-2H]2- closely resembles that of [ATP-H]-), while the spectral profile is affected to a greater extent by the variation of the molecular structure, i.e. the [AMP-H]- and [ADP-H]- photodepletion spectra display similar profiles while the [ATP-H]- spectrum is distinctive. The photodepletion cross-section also decreases for the ATP anions compared to both the AMP and ADP anions, reflecting a high intrinsic photostability of ATP versus both AMP and ADP. A range of photofragments are produced across the 4.0-5.8 eV spectral range for all of the ATP analogues studied. These fragments are primarily associated with fragmentation on the ground-state electronic surface, indicative of a statistical decay process where ultrafast decay is followed by ergodic dissociation. However, while the photofragments observed following photoexcitation of the monoanionic species, [AMP-H]- to [ADP-H]- to [ATP-H]- are entirely consistent with statistical decay, an additional group of photofragments are observed for the dianionic species, [ADP-2H]2- and [ATP-2H]2-, that we associate with electron detachment, and subsequent fragmentation of the resulting electron-detached photofragment. TDDFT calculations are presented to support the interpretation of the experimental data, and confirm that the electronic structure of the adenine moiety is relatively unperturbed by varying the overall charge.