Polarization‐Modulation Approaches to Reflection–Absorption Spectroscopy

Frey, Brian L.; Corn, Robert M.; Weibel, Stephen C.

doi:10.1002/0470027320.s2206

Cited by 42 publications

(61 citation statements)

References 22 publications

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“…PM-IRRAS exploits changes in electric field intensities near surfaces as a function of incident light polarization. 29 As a result, the technique provides enhanced sensitivity of infrared-active vibrations near a surface. This is ideal for analyzing the very thin (ca.…”

Section: Introductionmentioning

confidence: 99%

Structure of Aqueous Water Films on Textured −OH-Terminated Self-Assembled Monolayers

2015

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We report the thickness and interfacial molecular structure of thin (1-3 nm) aqueous films supported on hydroxyl-terminated self-assembled monolayers over a silver substrate. The water film structure is studied as a function of varying the monolayer's methylene chain lengths. Analysis techniques include ellipsometry, contact angle, and polarization modulation reflection adsorption infrared spectroscopy. The aqueous film thicknesses follow 4-mercaptobutanol (4-MBU) > 11-mercaptoundecanol (11-MUD) > 6-mercaptohexanol (6-MHE) > 9-mercaptononanol (9-MNO). Water contact angle measurements across the same surfaces are very similar; however, vibrational spectroscopic analysis of the films shows that intermolecular bonding patterns of D2O are significantly different from those of bulk D2O. This evokes unique interfacial molecular architectures for each of these films. The structural differences depend on the nature of the SAM structure and resulting water-SAM interactions, which are evident from PM-IRRAS data. Spectroscopic peak intensity ratios of ν(O-D) modes suggest more asymmetric hydrogen-bonded D2O character near 9-MNO surfaces, whereas 4-MDU, 6-MHE, and 11-MUD surfaces exhibit increasingly symmetric hydrogen-bonded D2O character. From this, we propose a model for film structure.

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Section: Introductionmentioning

confidence: 99%

Structure of Aqueous Water Films on Textured −OH-Terminated Self-Assembled Monolayers

2015

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“…The creation or destruction of surface species gives raise to negative or positive bands, respectively. In PM IRRAS, the polarization of the incident radiation is modulated between orthogonal components in the plane of incidence (p) and out of the plane of incidence (s) [2,3]. The electric field of the p-polarized beam is enhanced at the metal surface while the s-polarized beam almost vanishes and therefore is insensitive to the presence of the species at the interface.…”

Section: Introductionmentioning

confidence: 99%

PM IRRAS spectroelectrochemistry of layer-by-layer self-assembled polyelectrolyte multilayers

Tagliazucchi

Leo

Cadranel

et al. 2010

Journal of Electroanalytical Chemistry

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“…In the case of a high angle of incidence (grazing incidence), the absorption of p-polarized IR radiation by a thin layer on the metal surface is highly strengthened and even sub-monolayer quantities of chemisorbed molecules Nano Res. 2018, 11 (8): [4401][4402][4403][4404][4405][4406][4407][4408][4409][4410][4411] can be observed in the p-polarized spectrum [32]. In contrast, for s-polarized radiation at the same high angle of incidence, virtually zero absorption is observed.…”

Section: Introductionmentioning

confidence: 99%

“…In contrast, for s-polarized radiation at the same high angle of incidence, virtually zero absorption is observed. This specific relation between p-and s-polarized excitation light induces special surface selection rules which can be used to determine the geometry of the monolayer of molecules immobilized onto the metal substrate [32]. Therefore, molecular dipole moments alongside the highly reflecting surface are not excited by s-polarized radiation at any incidence angle [33][34][35].…”

Section: Introductionmentioning

confidence: 99%

Polarization effect in tip-enhanced infrared nanospectroscopy studies of the selective Y5 receptor antagonist Lu AA33810

et al. 2018

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A novel approach of combining conventional infrared spectroscopy (IR) and atomic force microscopy (AFM) is presented to better understand the behavior of a drug adsorbed on a metal substrate at the nanoscale level. Tip-enhanced infrared nanospectroscopy (TEIRA) was used for the first time to investigate Lu AA33810, a selective brain-penetrating Y5 receptor antagonist, after immobilization on gold nanoparticles (GNPs). Here, a gold coated AFM tip and gold substrate were used to obtain the near-field electromagnetic field trapping effect. Because of the huge signal enhancement, it was possible to obtain the spectral information regarding the self-assembled monolayer of the investigated molecule. The effect of two orthogonal polarizations (p-and s-polarization modulations) of the excitation laser beam on the spectral patterns is also discussed. The results show that there is a strong relationship between the state of polarization of the incident radiation and the relative infrared band intensities. Another factor affecting the observed spectral differences is the topology of the metal substrate, which may result in the induction of a cross-polarization effect. The performed analysis indicates that the C-C bond from the cyclohexyl group is oriented almost parallel to the metal surface. Conversely, the p-and s-polarized spectral variations suggest that the O=S=O angle is high enough to enable the simultaneous interaction of both oxygen atoms with the GNPs.

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Polarization‐Modulation Approaches to Reflection–Absorption Spectroscopy

Abstract: The sections in this article are Introduction to Polarization‐Modulation Reflection–Absorption Spectroscopy Experimental Considerations for the PM ‐ IRRAS Measurement Experimental Setup The P… Show more

Cited by 42 publications

References 22 publications

Structure of Aqueous Water Films on Textured −OH-Terminated Self-Assembled Monolayers

Structure of Aqueous Water Films on Textured −OH-Terminated Self-Assembled Monolayers

PM IRRAS spectroelectrochemistry of layer-by-layer self-assembled polyelectrolyte multilayers

Polarization effect in tip-enhanced infrared nanospectroscopy studies of the selective Y5 receptor antagonist Lu AA33810

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