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Quantifying Double-Layer Potentials at Liquid-Gas Interfaces from Vibrational Sum-Frequency Generation.

ABSTRACT: Vibrational sum-frequency generation (SFG) spectroscopy is demonstrated as a fast method to quantify variations of the electric double-layer potential ?0 at liquid-gas interfaces. For this, mixed solutions of nonionic tetraethyleneglycol-monodecylether (C10E4) and cationic hexadecyltrimethylammonium bromide (C16TAB) surfactants were investigated using SFG spectroscopy and a thin-film pressure balance (TFPB). Derjaguin-Landau-Verwey-Overbeek analysis of disjoining pressure isotherms obtained with the TFPB technique provides complementary information on ?0, which we apply to validate the results from SFG spectroscopy. By using a single ?0 value, we can disentangle ?(2) and ?(3) contributions to the O-H stretching modes of interfacial water molecules in the SFG spectra. Having established the latter, we show that unknown double-layer potentials at the liquid-gas interface from solutions with different C16TAB/C10E4 mixing ratios can be obtained from an analysis of SFG spectra and are in excellent agreement with the complementary results from the TFPB technique.

SUBMITTER: Garcia Rey N

PROVIDER: S-EPMC6354727 | biostudies-literature | 2019 Jan

REPOSITORIES: biostudies-literature

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Quantifying Double-Layer Potentials at Liquid-Gas Interfaces from Vibrational Sum-Frequency Generation.

García Rey Natalia N Weißenborn Eric E Schulze-Zachau Felix F Gochev Georgi G Braunschweig Björn B

The journal of physical chemistry. C, Nanomaterials and interfaces 20181220 2

Vibrational sum-frequency generation (SFG) spectroscopy is demonstrated as a fast method to quantify variations of the electric double-layer potential ϕ0 at liquid-gas interfaces. For this, mixed solutions of nonionic tetraethyleneglycol-monodecylether (C10E4) and cationic hexadecyltrimethylammonium bromide (C16TAB) surfactants were investigated using SFG spectroscopy and a thin-film pressure balance (TFPB). Derjaguin-Landau-Verwey-Overbeek analysis of ...[more]

PMID: 30713590

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Project description:Many photoinduced excited states' relaxation processes and chemical reactions occur at interfaces and surfaces, including charge transfer, energy transfer, proton transfer, proton-coupled electron transfer, configurational dynamics, conical intersections, etc. Of them, interactions of electronic and vibrational motions, namely, vibronic couplings, are the main determining factors for the relaxation processes or reaction pathways. However, time-resolved electronic-vibrational spectroscopy for interfaces and surfaces is lacking. Here we develop interface/surface-specific two-dimensional electronic-vibrational sum frequency generation spectroscopy (2D-EVSFG) for time-dependent vibronic coupling of excited states at interfaces and surfaces. We further demonstrate the fourth-order technique by investigating vibronic coupling, solvent correlation, and time evolution of the coupling for photoexcited interface-active molecules, crystal violet (CV), at the air/water interface as an example. The two vibronic absorption peaks for CV molecules at the interface from the 2D-EVSFG experiments were found to be more prominent than their counterparts in bulk from 2D-EV. Quantitative analysis of the vibronic peaks in 2D-EVSFG suggested that a non-Condon process participates in the photoexcitation of CV at the interface. We further reveal vibrational solvent coupling for the zeroth level on the electronic state with respect to that on the ground state, which is directly related to the magnitude of its change in solvent reorganization energy. The change in the solvent reorganization energy at the interface is much smaller than that in bulk methanol. Time-dependent center line slopes (CLSs) of 2D-EVSFG also showed that kinetic behaviors of CV at the air/water interface are significantly different from those in bulk methanol. Our ultrafast 2D-EVSFG experiments not only offer vibrational information on both excited states and the ground state as compared with the traditional doubly resonant sum frequency generation and electronic-vibrational coupling but also provide vibronic coupling, dynamical solvent effects, and time evolution of vibronic coupling at interfaces.

Dataset Information

Quantifying Double-Layer Potentials at Liquid-Gas Interfaces from Vibrational Sum-Frequency Generation.

Publications

Quantifying Double-Layer Potentials at Liquid-Gas Interfaces from Vibrational Sum-Frequency Generation.

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