Formulas for the Analysis of the Surface SFG Spectrum and Transformation Coefficients of Cartesian SFG Tensor Components

Hirose, Chiaki; Akamatsu, Naotoshi; Domen, Kazunari

doi:10.1366/0003702924124385

Cited by 375 publications

(500 citation statements)

References 25 publications

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“…By mathematically transforming the hyperpolarizability elements of the SS and the AS of the methyl group of MSA from molecular coordinates to the laboratory coordinate system via Euler angle rotations, it has been shown previously that the SF response from the SS and the AS of CH modes from methyl groups of C 3v symmetry are of opposite phase. 36 39,40 That is what is observed here.…”

Section: Vsf Of the Vapor/water Interfacesupporting

confidence: 89%

Surface Structural Studies of Methanesulfonic Acid at Air /Aqueous Solution Interfaces Using Vibrational Sum Frequency Spectroscopy

2000

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Atmospheric gas phase species such as methanesulfonic acid (MSA) are adsorbed and accommodated into atmospheric aqueous-phase aerosols, and in some cases MSA is thought to be produced via aerosol surface chemistry. The studies described herein probe the surface molecular structure of MSA at aqueous solution surfaces using surface vibrational sum frequency spectroscopy (VSFS). In the studies presented here, it is shown that MSA partitions to the surface and that the surface MSA has a preferred orientation in which the methyl group points away from the liquid surface. The surrounding surface water structure is significantly affected by the adsorption of MSA. Small amounts of MSA at the surface of water cause the water molecule vibrational stretching modes to shift to lower energies. This shift is indicative of stronger coupling between the water molecules caused by the presence of MSA. Additional VSF studies show that MSA is effectively displaced by sulfuric acid at an aqueous surface. The structural details presented here may have implications for understanding atmospheric aerosol growth properties.

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Section: Vsf Of the Vapor/water Interfacesupporting

confidence: 89%

Surface Structural Studies of Methanesulfonic Acid at Air /Aqueous Solution Interfaces Using Vibrational Sum Frequency Spectroscopy

2000

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“…We observed three dips in the ER condition rather than peaks. 29 This difference in φ results from both the change in the Fresnel coeffcients 35,36 and the contribution of the gold/CaF2 interface to χ NR (2) . 24 We normalized this spectrum by that for a GaAs surface; the susceptibility of the GaAs surface is independent of the wavelength in the region studied and we hence can measure the IR envelope.…”

Section: Tir-bbsfgmentioning

confidence: 99%

Total-internal-reflection Broad-bandwidth Sum Frequency Generation Spectroscopy of Hexadecanethiol Adsorbed on Thin Gold Film Deposited on CaF, 2

et al. 2003

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IntroductionFor the study of surface phenomena at various interfaces, the total internal reflection (TIR) condition has been used in a number of spectroscopic measurements, 1 such as fluorometry, 2-9 surface enhanced infrared spectroscopy (SEIRA), [10][11][12] second harmonic generation, [13][14][15][16][17][18][19][20][21] and sum frequency generation (SFG). [22][23][24][25] There are two advantages when one uses the TIR condition. First, both incident light to the interface and reflected light or generated light from the interface travel in only one of the two phases adjacent to the interface, which circumvents bulk absorption by the other phase. One corollary is the freedom of changing the composition of the adjacent phase that has a lower refractive index. Second, high sensitivity to the interfaces can be achieved owing to the enhancement of the electric field at the interfaces. 1 The TIR arrangement can be employed at metal interfaces if a very thin metal film is used to avoid the absorption of light. It has been successfully employed to detect adsorbed species on metal in the SEIRA, where the thickness of the metal film is about 10 nm on a transparent substrate. [10][11][12] Recently, Williams et al. showed that the TIR arrangement can also be employed to detect SFG signals from alkanethiols adsorbed on a thin gold film. 24 However, detailed analysis of the sum frequency vibrational spectra has not been reported. SFG in the TIR arrangement has some potential as a powerful tool to study molecular orientations at metal/liquid interfaces, such as electrochemical interfaces, because it is free from bulk absorption and has interfacial sensitivity in the order of nanometers. Unlike surface plasmon resonance and capacitance measurements that have been used as sensitive means of detecting adsorption and molecular interaction at the interfaces, TIR-SFG will enable us to obtain molecular information on the solution side of the interfaces. One drawback of the TIR arrangement is the roughness of the metal surfaces. The roughness is prerequisite for high sensitivity and can complicate the interpretation of the experimental data because of the orientational distribution of molecules in comparison with those adsorbed on a single crystal surface. It is therefore of crucial importance to assess the degree of the variation in orientation of molecules.By using broad-bandwidth sum frequency generation (BBSFG) [26][27][28] we recently analyzed the orientation of alkanethiols adsorbed on Au(111). 29It is worthwhile to examine the applicability of BBSFG in the TIR condition at metal interfaces to obtain SFG spectra with higher resolution. In the present paper, we report the results of TIR-BBSFG measurements for hexadecanethiol (HDT) adsorbed on a thin gold film on CaF2. We will show that BBSFG can be successfully employed in the orientation analysis of the HDT molecules and that the methyl groups of HDT are much more randomly orientated than those on Au(111) on mica. Experimental SubstrateA hemicylindrical CaF2 prism (Pier Optic...

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“…[22][23][24][25] The VSF spectra were obtained for water surfaces at an atmospheric pressure of ~1 atm and at ~ 21° C. HPLC grade water or Nanopure water (18 MÜ) was utilized in these studies. The laser system [26] …”

mentioning

confidence: 99%

Discovery of Oriented Gaseous Water Molecules in the Vapor-Liquid Interface of Water

Allen¹,

Raymond²,

Brown³

et al. 2000

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Formulas for the Analysis of the Surface SFG Spectrum and Transformation Coefficients of Cartesian SFG Tensor Components

Cited by 375 publications

References 25 publications

Surface Structural Studies of Methanesulfonic Acid at Air /Aqueous Solution Interfaces Using Vibrational Sum Frequency Spectroscopy

Surface Structural Studies of Methanesulfonic Acid at Air /Aqueous Solution Interfaces Using Vibrational Sum Frequency Spectroscopy

Total-internal-reflection Broad-bandwidth Sum Frequency Generation Spectroscopy of Hexadecanethiol Adsorbed on Thin Gold Film Deposited on CaF, 2

Discovery of Oriented Gaseous Water Molecules in the Vapor-Liquid Interface of Water

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