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

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

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


Authors

Maria Elena Castellani

Davide Avagliano



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

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Accepted Journal Article (620 Kb)
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Copyright 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




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