Structural definition of the BIL and DL: a new universal methodology to rationalize non-linear χ(2)(ω) SFG signals at charged interfaces, including χ(3)(ω) contributions

文献信息

发布日期 2018-01-23
DOI 10.1039/C7CP06110B
影响因子 3.676
作者

Simone Pezzotti, Daria Ruth Galimberti, Y. Ron Shen, Marie-Pierre Gaigeot


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摘要

This work provides unambiguous definitions from theoretical simulations of the two interfacial regions named the BIL (binding interfacial layer) and DL (diffuse layer) at charged solid/water and air/water interfaces. The BIL and DL nomenclature follows the pioneering work of Wen et al. [Phys. Rev. Lett. 2016, 116, 016101]. Our definitions are based on the intrinsic structural properties of water only. Knowing the BIL and DL interfacial regions, one is then able to deconvolve the χ(2)(ω) non-linear SFG (sum frequency generation) response into χ(2)BIL(ω) and χ(2)DL(ω) contributions, thus providing a detailed molecular interpretation of these signals and of the measured total SFG. We furthermore show that the χ(2)DL(ω) spectrum arises from the χ(3)(ω) non-linear third order contribution of bulk liquid water, here calculated for several charged interfaces and shown to be universal. The χ(2)DL(ω) contribution therefore has the same origin in terms of molecular normal modes at any charged interface. The molecular interpretation of χ(2)BIL(ω) is hence at the heart of the unambiguous molecular comprehension and interpretation of the measured total SFG signal at any charged interface.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
自引率: 10.3%
年发文量: 3036

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