We use cookies to ensure that we give you the best experience on our website. By continuing to browse this repository, you give consent for essential cookies to be used. You can read more about our Privacy and Cookie Policy.

Durham Research Online
You are in:

Site-Specific Photo-oxidation of the Isolated Adenosine-5′-triphosphate Dianion Determined by Photoelectron Imaging

Castellani, Maria Elena and Avagliano, Davide and González, Leticia and Verlet, Jan R. R. (2020) 'Site-Specific Photo-oxidation of the Isolated Adenosine-5′-triphosphate Dianion Determined by Photoelectron Imaging.', The journal of physical chemistry letters., 11 (19). pp. 8195-8201.


Photoelectron imaging of the isolated adenosine-5′-triphosphate dianion excited to the 1ππ* states reveals that electron emission is predominantly parallel to the polarization axis of the light and arises from subpicosecond electron tunneling through the repulsive Coulomb barrier (RCB). The computed RCB shows that the most probable electron emission site is on the amino group of adenine. This is consistent with the photoelectron imaging: excitation to the 1ππ* states leads to an aligned ensemble distributed predominantly parallel to the long axis of adenine; the subsequent electron tunneling site is along this axis; and the negatively charged phosphate groups guide the outgoing electron mostly along this axis at long range. Imaging of electron tunneling from polyanions combined with computational chemistry may offer a general route for probing the intrinsic photo-oxidation site and dynamics as well as the overall structure of complex isolated species.

Item Type:Article
Full text:(AM) Accepted Manuscript
Download PDF
Publisher Web site:
Publisher statement:This document is the Accepted Manuscript version of a Published Work that appeared in final form in The journal of physical chemistry letters., copyright © 2020 American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see
Date accepted:04 September 2020
Date deposited:06 May 2021
Date of first online publication:04 September 2020
Date first made open access:04 September 2021

Save or Share this output

Look up in GoogleScholar