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

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

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
• Electronic ISSN: 1948-7185
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 7
• Issue: 20
• Pages: 4079-4085
• DOI: https://doi.org/10.1021/acs.jpclett.6b01985
• Public URL: https://durham-repository.worktribe.com/output/1402072