Next Article in Journal
A Climatological Study of Western Mediterranean Medicanes in Numerical Simulations with Explicit and Parameterized Convection
Previous Article in Journal
Re-Examination of the Decadal Change in the Relationship between the East Asian Summer Monsoon and Indian Ocean SST
Previous Article in Special Issue
The FuGas 2.3 Framework for Atmosphere–Ocean Coupling: Comparing Algorithms for the Estimation of Solubilities and Gas Fluxes
Article Menu

Export Article

Open AccessArticle
Atmosphere 2018, 9(10), 396;

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
Authors to whom correspondence should be addressed.
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)
Full-Text   |   PDF [2659 KB, uploaded 11 October 2018]   |  


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

Figure 1

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).

Share & Cite This Article

MDPI and ACS Style

Pezzotti, S.; Gaigeot, M.-P. Spectroscopic BIL-SFG Invariance Hides the Chaotropic Effect of Protons at the Air-Water Interface. Atmosphere 2018, 9, 396.

Show more citation formats Show less citations formats

Note that from the first issue of 2016, MDPI journals use article numbers instead of page numbers. See further details here.

Related Articles

Article Metrics

Article Access Statistics



[Return to top]
Atmosphere EISSN 2073-4433 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
Back to Top