Ultrafast Dynamics of the Isolated Adenosine-5′-triphosphate Dianion Probed by Time-Resolved Photoelectron Imaging

Castellani, Maria Elena; Avagliano, Davide; Verlet, Jan R.R.

Abstract

The excited state dynamics of the doubly deprotonated dianion of adenosine-5′-triphosphate, [ATP–H2]2–, has been spectroscopically explored by time-resolved photoelectron spectroscopy following excitation at 4.66 eV. Time-resolved photoelectron spectra show that two competing processes occur for the initially populated 1ππ* state. The first is rapid electron emission by tunneling through a repulsive Coulomb barrier as the 1ππ* state is a resonance. The second is nuclear motion on the 1ππ* state surface leading to an intermediate that no longer tunnels and subsequently decays by internal conversion to the ground electronic state. The spectral signatures of the features are similar to those observed for other adenine-derivatives, suggesting that this nucleobase is quite insensitive to the nearby negative charges localized on the phosphates, except of course for the appearance of the additional electron tunneling channel, which is open in the dianion.

Citation

Castellani, M. E., Avagliano, D., & Verlet, J. R. (2021). Ultrafast Dynamics of the Isolated Adenosine-5′-triphosphate Dianion Probed by Time-Resolved Photoelectron Imaging. The Journal of Physical Chemistry A, 125(17), 3646-3652. https://doi.org/10.1021/acs.jpca.1c01646

• Journal Article Type: Article
• Online Publication Date: Apr 22, 2021
• Publication Date: May 6, 2021
• Deposit Date: May 6, 2021
• Publicly Available Date: Apr 22, 2022
• Journal: The Journal of Physical Chemistry A
• Print ISSN: 1089-5639
• Electronic ISSN: 1520-5215
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 125
• Issue: 17
• Pages: 3646-3652
• DOI: https://doi.org/10.1021/acs.jpca.1c01646
• Public URL: https://durham-repository.worktribe.com/output/1248483