Second Harmonic and Sum-Frequency Generation from Aqueous Interfaces Is Modulated by Interference

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• 作者：Grazia Gonella ; Cornelis Lütgebaucks ; Alex G. F. de Beer ; Sylvie Roke
• 刊名：Journal of Physical Chemistry C
• 出版年：2016
• 出版时间：May 5, 2016
• 年：2016
• 卷：120
• 期：17
• 页码：9165-9173
• 全文大小：497K
• 年卷期：0
• ISSN：1932-7455

文摘

The interfacial region of aqueous systems also known as the electrical double layer can be characterized on the molecular level with second harmonic and sum-frequency generation (SHG/SFG). SHG and SFG are surface specific methods for isotropic liquids. Here, we model the SHG/SFG intensity in reflection, transmission, and scattering geometry taking into account the spatial variation of all fields. We show that, in the presence of a surface electrostatic field, interference effects, which originate from oriented water molecules on a length scale over which the potential decays, can strongly modify the probing depth as well as the expected intensity at ionic strengths <10^–3 M. For reflection experiments this interference phenomenon leads to a significant reduction of the SHG/SFG intensity. Transmission mode experiments from aqueous interfaces are hardly influenced. For SHG/SFG scattering experiments the same interference leads to an increase in intensity and to modified scattering patterns. The predicted scattering patterns are verified experimentally.