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Issue 25, 2017
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Surface-specific vibrational spectroscopy of the water/silica interface: screening and interference

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Abstract

Surface-specific vibrational sum-frequency generation spectroscopy (V-SFG) is frequently used to obtain information about the molecular structure at charged interfaces. Here, we provide experimental evidence that not only screening of surface charges but also interference limits the extent to which V-SFG probes interfacial water at sub-mM salt concentrations. As a consequence, V-SFG yields information about the ∼single monolayer interfacial region not only at very high ionic strength, where the surface charge is effectively screened, but also for pure water due to the particularly large screening length at this low ionic strength. At these low ionic strengths, the large screening lengths cause destructive interference between contributions in the surface region. A recently proposed theoretical framework near-quantitatively describes our experimental findings by considering only interference and screening. However, a comparison between NaCl and LiCl reveals ion specific effects in the screening efficiency of different electrolytes. Independent of electrolyte, the hydrogen bonding strength of water right at the interface is enhanced at high electrolyte concentrations.

Graphical abstract: Surface-specific vibrational spectroscopy of the water/silica interface: screening and interference

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Publication details

The article was received on 07 Apr 2017, accepted on 09 Jun 2017 and first published on 13 Jun 2017


Article type: Paper
DOI: 10.1039/C7CP02251D
Citation: Phys. Chem. Chem. Phys., 2017,19, 16875-16880
  • Open access: Creative Commons BY license
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    Surface-specific vibrational spectroscopy of the water/silica interface: screening and interference

    J. Schaefer, G. Gonella, M. Bonn and E. H. G. Backus, Phys. Chem. Chem. Phys., 2017, 19, 16875
    DOI: 10.1039/C7CP02251D

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