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

Castellani, Maria Elena and Avagliano, Davide and Verlet, Jan R. R. (2021) 'Ultrafast Dynamics of the Isolated Adenosine-5′-triphosphate Dianion Probed by Time-Resolved Photoelectron Imaging.', Journal of physical chemistry A., 125 (17). pp. 3646-3652.

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.

Item Type:Article
Full text:(AM) Accepted Manuscript
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Status:Peer-reviewed
Publisher Web site:https://doi.org/10.1021/acs.jpca.1c01646
Publisher statement:This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of physical chemistry A, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.jpca.1c01646
Date accepted:No date available
Date deposited:06 May 2021
Date of first online publication:22 April 2021
Date first made open access:22 April 2022

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