Charge Transfer to Solvent Dynamics at the Ambient Water/Air Interface

Nowakowski, P.J.; Woods, D.A.; Verlet, J.R.R.

doi:10.1021/acs.jpclett.6b01985

Charge Transfer to Solvent Dynamics at the Ambient Water/Air Interface

Nowakowski, P.J.; Woods, D.A.; Verlet, J.R.R.

Authors

P.J. Nowakowski

D.A. Woods

Professor Jan Verlet j.r.r.verlet@durham.ac.uk
Professor

Abstract

Electron-transfer reactions at ambient aqueous interfaces represent one of the most fundamental and ubiquitous chemical reactions. Here the dynamics of the charge transfer to solvent (CTTS) reaction from iodide was probed at the ambient water/air interface by phase-sensitive transient second-harmonic generation. Using the three allowed polarization combinations, distinctive dynamics assigned to the CTTS state evolution and to the subsequent solvating electron-iodine contact pair have been resolved. The CTTS state is asymmetrically solvated in the plane of the surface, while the subsequent electron solvation dynamics are very similar to those observed in the bulk, although slightly faster. Between 3 and 30 ps, a small phase shift distinguishes an electron bound in a contact pair with iodine and a free hydrated electron at the water/air interface. Our results suggest that the hydrated electron is fully solvated in a region of reduced water density at the interface.

Citation

Nowakowski, P., Woods, D., & Verlet, J. (2016). Charge Transfer to Solvent Dynamics at the Ambient Water/Air Interface. Journal of Physical Chemistry Letters, 7(20), 4079-4085. https://doi.org/10.1021/acs.jpclett.6b01985

Journal Article Type	Article
Acceptance Date	Sep 29, 2016
Online Publication Date	Oct 3, 2016
Publication Date	Oct 20, 2016
Deposit Date	Oct 31, 2016
Publicly Available Date	Sep 29, 2017
Journal	Journal of Physical Chemistry Letters
Publisher	American Chemical Society
Peer Reviewed	Peer Reviewed
Volume	7
Issue	20
Pages	4079-4085
DOI	https://doi.org/10.1021/acs.jpclett.6b01985

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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 letters, 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.jpclett.6b01985.