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Atmosphere 2018, 9(10), 396; https://doi.org/10.3390/atmos9100396

Spectroscopic BIL-SFG Invariance Hides the Chaotropic Effect of Protons at the Air-Water Interface

LAMBE UMR8587, Laboratoire Analyse et Modélisation pour la Biologie et l’Environnement, Université d’Evry val d’Essonne, Université Paris-Saclay, Blvd F. Mitterrand, Bat Maupertuis, 91025 Evry, France
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Received: 13 September 2018 / Revised: 1 October 2018 / Accepted: 3 October 2018 / Published: 11 October 2018
(This article belongs to the Special Issue Physical Chemistry of the Air-Water Interface)
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Abstract

The knowledge of the water structure at the interface with the air in acidic pH conditions is of utmost importance for chemistry in the atmosphere. We shed light on the acidic air-water (AW) interfacial structure by DFT-MD simulations of the interface containing one hydronium ion coupled with theoretical SFG (Sum Frequency Generation) spectroscopy. The interpretation of SFG spectra at charged interfaces requires a deconvolution of the signal into BIL (Binding Interfacial Layer) and DL (Diffuse Layer) SFG contributions, which is achieved here, and hence reveals that even though H 3 O + has a chaotropic effect on the BIL water structure (by weakening the 2D-HBond-Network observed at the neat air-water interface) it has no direct probing in SFG spectroscopy. The changes observed experimentally in the SFG of the acidic AW interface from the SFG at the neat AW are shown here to be solely due to the DL-SFG contribution to the spectroscopy. Such BIL-SFG and DL-SFG deconvolution rationalizes the experimental SFG data in the literature, while the hydronium chaotropic effect on the water 2D-HBond-Network in the BIL can be put in perspective of the decrease in surface tension at acidic AW interfaces. View Full-Text
Keywords: acidic air-water interface; DFT-MD; ab-initio; SFG; BIL/DL; 2D-HB-Network acidic air-water interface; DFT-MD; ab-initio; SFG; BIL/DL; 2D-HB-Network
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).
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Pezzotti, S.; Gaigeot, M.-P. Spectroscopic BIL-SFG Invariance Hides the Chaotropic Effect of Protons at the Air-Water Interface. Atmosphere 2018, 9, 396.

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