Infrared-visible Sum Frequency Generation Spectroscopy Research Articles

In Situ Nanoscale Characterization of Water Penetration through Plasma Polymerized Coatings.

The search continues for means of making quick determinations of the efficacy of a coating for protecting a metal surface against corrosion. One means of reducing the time scale needed to differentiate the performance of different coatings is to draw from nanoscale measurements inferences about macroscopic behavior. Here we connect observations of the penetration of water into plasma polymerized (PP) protective coatings and the character of the interface between the coating and an oxide-coated aluminum substrate or model oxide-coated silicon substrate to the macroscopically observable corrosion for those systems. A plasma polymerized film from hexamethyldisiloxane (HMDSO) monomer is taken as illustrative of a hydrophobic coating, while a PP film from maleic anhydride (MA) is used as a characteristically hydrophilic coating. The neutron reflectivity (NR) of films on silicon oxide coated substrates shows that water moves more readily through the hydrophilic PP-MA film. Off-specular X-ray scattering indicates the PP-MA film on aluminum is less conformal with the substrate than is the PP-HMDSO film. Measurements with infrared-visible sum frequency generation spectroscopy (SFG), which probes the chemical nature of the interface, make clear that the chemical interactions between coating and aluminum oxide are disrupted by interfacial water. With this water penetration and interface disruption, macroscopic corrosion can occur much more rapidly. An Al panel coated with PP-MA corrodes after 1 day in salt spray, while a similarly thin (∼30 nm) PP-HMDSO coating protects an Al panel for a period on the order of one month.

Effect of Surface Energy on Freezing Temperature of Water.

Previous studies have found that superhydrophobic surfaces are effective in delaying freezing of water droplets. However, the freezing process of water droplets on superhydrophobic surfaces depends on factors such as droplet size, surface area, roughness, and cooling rate. The role of surface energy, independent of any other parameters, in delaying freezing of water is not understood. Here, we have used infrared-visible sum frequency generation spectroscopy (SFG) to study the freezing of water next to solid substrates with water contact angles varying from 5° to 110°. We find that the freezing temperature of water decreases with increasing surface hydrophobicity only when the sample volume is small (∼10 μL). For a larger volume of water (∼300 μL), the freezing temperature is independent of surface energy. For water next to the surfaces with contact angle ≥54°, we observe a strong SFG peak associated with highly coordinated water. This research sheds new light on understanding the key factors in designing new anti-icing coatings.

Interfacial Water at Polyurethane-Sapphire Interface.

Infrared-visible sum frequency generation spectroscopy (SFG) was used to directly probe water between polyurethane (PU) and sapphire substrates after exposing samples to liquid water and water vapor. For liquid water, the observation of SFG peaks associated with H2O bands (3000-3400 cm(-1)) and D2O bands (2300-2600 cm(-1)) indicated water molecules diffused to the buried interface and existed in the form of a hydrogen-bonded water network. The water layer disrupted interactions between polyurethane and sapphire. When PU films were exposed to water vapor, the SFG peak intensities of PU hydrocarbon and sapphire hydroxyl groups changed significantly, which suggested water molecules had reached the interface. However, no hydrogen-bonded water bands were present; instead, the H2O peak at 3550 cm(-1) and D2O peaks (2600-2700 cm(-1)) were observed. We assigned these peaks to low-coordination water molecules or hydroxyl groups hydrogen bonded with carboxyl groups of PU at the interface. The water molecules did not form a uniform layer at the interface and as a consequence did not completely disrupt the PU/sapphire interactions. These results provide important implications for understanding interfacial adhesion, coatings, and corrosion.

Polarization entanglement of sum-frequency photons: A tool to probe the Markovian limit

The article addresses the possibility of entanglement-specific infrared-visible sum-frequency generation spectroscopy. In the case of an anisotropic interface, it is possible to employ SSS and PSS polarizations to detect responses not only specific to ${\ensuremath{\chi}}_{YYY}$ and ${\ensuremath{\chi}}_{XYY}$ nonlinearities, but also to higher-order ${\ensuremath{\chi}}_{(YYY)(XYY)}$ and ${\ensuremath{\chi}}_{(XYY)(YYY)}$ nonlinearities. Using quantum mechanical studies of the rhenium complex $[\mathrm{Re}{(\mathrm{OH})}_{3}{(\mathrm{CO})}_{3}]$ as a molecular model, we demonstrate that if such complexes would form an anisotropic orientational distribution at a surface, under the considered geometry and the polarization settings, we may prepare quantum correlated $\mathrm{C}=\mathrm{O}$ vibrational states to emit polarization-entangled photons. Accordingly, we explore the possibility of a polarization-measurement protocol to extract spectral signatures of the entangled states. The response would be informative on intramolecular interactions. As a result, we discuss the possible practical implications in probing dynamics at interfaces, and different opportunities in the preparation of entangled vibrational states of quantified fidelity.

Breaking the Symmetry of Ions at the Air–Water Interface

In this Article, we investigate the impact of the fluid-air interface on the dissolved electrolyte potassium ferrocyanide K4[Fe(CN)6] by infrared-visible sum-frequency generation spectroscopy (SFG) and surface tension measurements. SFG is a surface specific nonlinear optical technique that records the vibrational spectrum of the adsorbed species with little to no contribution from the bulk phase. According to the selection rules, only modes which are simultaneously Raman and Infrared active can contribute to the SFG spectrum. Since [Fe(CN)6]4– belongs to the point group Oh, no vibrational mode is SFG active, unless a deformation takes place. Our spectra provide experimental evidence for a symmetry reduction of the ions at the interface to subgroups with no center of inversion. The distortion of the ions is the direct consequence of the asymmetric environment at the interface and is further discussed in this paper. The SFG spectra of the interfacial water were used to gain further insights in the distribution of the ions at the interface. Furthermore, the combined data of the surface tension equilibrium isotherm and the SFG spectra suggest a nonmonotonous interfacial concentration profile of the ion.

Interfacial Segregation in Polymer Blends Driven by Acid–Base Interactions

Infrared-visible sum frequency generation spectroscopy (SFG) was used to measure the interfacial concentrations of poly(methyl methacrylate) (PMMA)/polystyrene (PS) blends next to a sapphire substrate. The acid-base interactions of carbonyl groups of PMMA with the hydroxyl groups on the sapphire drive the interfacial segregation of PMMA next to the sapphire substrate. Using the shift of sapphire surface OH peaks, we have determined the difference in interfacial energy between the PMMA/sapphire and the PS/sapphire to be ~44-45 mJ/m(2). These results highlight the importance of acid-base interactions and their role in controlling the interfacial segregation next to solid substrates in polymer blends.

Freezing and Melting of Salt Hydrates Next to Solid Surfaces Probed by Infrared–Visible Sum Frequency Generation Spectroscopy

Understanding the freezing of salt solutions near solid surfaces is important in many scientific fields. Here we use sum frequency generation (SFG) spectroscopy to study the freezing of a NaCl solution next to a sapphire substrate. During cooling we observe two transitions. The first corresponds to segregation of concentrated brine next to the sapphire surface as we cool the system down to the region where ice and brine phases coexist. At this transition, the intensity of the ice-like peak decreases, suggesting the disruption of hydrogen-bonding by sodium ions. The second transition corresponds to the formation of NaCl hydrates with abrupt changes in both the SFG intensity and the sharpness of spectral peaks. The similarity in the position of the SFG peaks with those observed using IR and Raman spectroscopy indicates the formation of NaCl·2H2O crystals next to the sapphire substrate. The melting temperatures of the hydrates are very similar to those reported for bulk NaCl·2H2O. This study enhances our understanding of nucleation and freezing of salt solutions on solid surfaces and the effects of salt ions on the structure of interfacial ice.

Freezing of Water Next to Solid Surfaces Probed by Infrared–Visible Sum Frequency Generation Spectroscopy

Ice formation next to solid surfaces is important in many biological, materials, and geological phenomena and may be a factor in how they impact various technologies. We have used sum frequency generation (SFG) spectroscopy to study the structure of ice as well as the freezing and melting transition temperatures of water in contact with sapphire substrates. We have observed that the structure of ice and water are a function of pH and the surface charge of the sapphire substrate. At low pH, we observed an increase in the SFG signal subsequent to ice formation. Contrary to expectations, at pH 9.8, corresponding to a negatively charged surface, the intensity of the ice SFG signal is about 10 times lower than that of water. Recent simulation studies have suggested that charge transfer is important for the high intensity of the ice peak at the ice-air interface. We believe that the segregation of sodium ions next to the negatively charged sapphire substrate may be responsible for disrupting the charge transfer and stitching bilayer at high pH, providing a plausible explanation for the experimental observations. Even though the structure of water and ice are affected by pH, the freezing and melting transition temperatures are independent of the surface charge. This report offers a unique insight on how ions next to solid surfaces could influence the structure of ice.

Contact of Oil with Solid Surfaces in Aqueous Media Probed Using Sum Frequency Generation Spectroscopy

We have studied the interface between hexadecane droplets and sapphire substrates in water using infrared-visible sum frequency generation spectroscopy (SFG). At high pH and above the isoelectric point of the sapphire substrate, the hexadecane drop is repelled due to electrostatic forces. The SFG measurements are consistent with the observation that a thick layer of water is present between the oil and the sapphire substrate. Below the isoelectric point of the sapphire substrate, the hexadecane drops stick to the sapphire surface. Surprisingly, the SFG results show the presence of a thin layer of water between hexadecane drop and the sapphire substrate. At this contact interface, we observe contributions to the SFG signal from both the hexadecane/water and water/sapphire interfaces. The reasons for the presence of a thin water layer with adhesive contact can be explained due to weaker repulsive double layer and the attractive van der Waals interactions.

Interference Effect from Buried Interfaces Investigated by Angular-Dependent Infrared−Visible Sum Frequency Generation Technique

Infrared-visible sum frequency generation spectroscopy (SFG) in conjunction with total internal reflection geometry (TIR) has been demonstrated as a powerful technique to study buried polymer interfaces. We have developed a theoretical model using linear and nonlinear boundary conditions to calculate the SFG signals as a function of incident angles and thickness of the polymer films. The validity of this model is tested using a polystyrene film (PS) coated on a sapphire prism. This PS film is exposed to heneicosane (C21H44) above and below its melting temperature. At temperatures greater than Tm, the SFG contributions from both interfaces (PS/sapphire and alkane/PS) are comparable and we observe strong interference effects. At temperatures below Tm, the SFG signals are dominated by the methyl signals of all-trans heneicosane molecules at the alkane/PS interface. The theoretical model is able to accurately capture the angle and thickness dependence of the SFG signal and provides a valuable tool to accurate...

Sum-frequency generation spectroscopy of self-assembled structures of Guanosine 5′-monophosphate on mica

The structure and ordering of Guanosine 5′-monophosphate (GMP) films self-assembled on mica from GMP salt solutions were studied by infrared-visible sum-frequency generation spectroscopy (IR-VIS SFG) and atomic force microscopy (AFM). We find that the surface self-assembly of GMP can be tuned through the concentration of the GMP solution as well as the nature of the counter ion. At low concentrations of the ammonium and the sodium GMP salt solutions, the self-assembled films are very similar, while at higher concentrations the SFG signal of ammonium GMP samples is dominated by a contribution not originating from azimuthally symmetric layers, which signifies that a helical bulk structure might be present.

Study of self-assembled triethoxysilane thin films made by casting neat reagents in ambient atmosphere

We studied four trialkoxysilane thin films, fabricated via self-assembly by casting neat silane reagents onto hydrophilic SiO x /Si substrates in the ambient. This drop-casting method is simple, yet rarely studied for the production of silane self-assembled monolayers (SAMs). Various ex-situ techniques were utilized to systematically characterize the growth process: Ellipsometry measurements can monitor the evolution of film thickness with silanization time; water droplet contact angle measurements reveal the wettability; the change of surface morphology was followed by Atomic Force Microscopy; the chemical identity of the films was verified by Infrared–Visible Sum Frequency Generation spectroscopy. We show that the shorter carbon chain (propyl-) or branched (2-(diphenylphosphino)ethyl-) silane SAMs exhibit poor ordering. In contrast, longer carbon chain (octadecyl and decyl) silanes form relatively ordered monolayers. The growth of the latter two cases shows Langmuir-like kinetics and a transition process from lying-down to standing-up geometry with increasing coverage.

Confinement-Induced Ordering of Alkanes between an Elastomer and a Solid Surface

We have studied the molecular structure of liquid alkanes confined between a flexible elastomeric poly(dimethyl siloxane) lens and a rigid sapphire substrate using surface-sensitive infrared-visible sum frequency generation spectroscopy. The reduction in the gauche defects suggests ordering of liquid alkanes under confinement. The cooling of confined liquid below the freezing temperature leads to crystallization with alkane molecules lying on the substrate with the symmetry axis parallel to the surface normal. This structure is very different from the bulk alkane crystals next to sapphire or air interfaces.

Direct Probe of Interfacial Structure during Mechanical Contact between Two Polymer Films Using Infrared Visible Sum Frequency Generation Spectroscopy

ABSTRACT Infrared-visible sum frequency generation spectroscopy (SFG) has been used to study the interface between poly(vinyl-N-octadecylcarbamate-co-vinyl acetate) (PVNODC) and polystyrene (PS) films during mechanical contact. The films were contacted using a deformable semispherical poly(dimethylsiloxane) (PDMS) lens that can be easily adapted to incorporate friction and adhesion force measurements. A strong methyl symmetric peak and Fermi resonance band associated with the alkyl side chains of PVNODC are observed in the SFG spectrum. This suggests that the interface structure during mechanical contact is more ordered than the structure observed for PS/PVNODC bilayer films annealed above the melting and glass transition temperatures of PVNODC and PS. Complementary contact mechanics measurements reveal a small adhesion hysteresis supporting our hypothesis that the interface structure during mechanical contact is not significantly different from the structure of the air interfaces before contact.

Molecule orientation in self-assembled monolayers determined by infrared-visible sum-frequency generation spectroscopy

The molecular orientation in self-assembled monolayers of thiophenol (TP) on Ag(1 1 1) and of para-nitroanilino-dodecane-thiol (NAT) on Au was investigated by infrared-visible sum-frequency generation between 500 and 1500 cm−1. Ab initio calculations were performed to determine the interface nonlinear response. The combined experimental and theoretical results reveal that the S–C bond of TP is tilted 37∘ from the Ag(1 1 1) surface normal, with the aromatic ring plane perpendicular to the surface. On Au, the tilt angle of the NAT molecule stabilizes below 60∘ at the end of film growth.

Sum-frequency generation spectroscopy applied to model biosensors systems

Vibrational information recorded by infrared-visible sum frequency generation spectroscopy was used to study the adsorption of a derivated vitamin (biocytin) on different substrates and its subsequent reaction with a protein (avidin). No reaction is observed on metallic substrates. When the experiments are carried out with a CaF 2 substrate in the total internal reflection configuration, significant changes of the CH and NH vibrations can be related to the specific bonding of avidin to biocytin.

Probing the charge-transfer state of CO on Pt(111) by two-dimensional infrared-visible sum frequency generation spectroscopy

The lowest charge-transfer band of CO on Pt(111) was identified using two-dimensional infrared-visible sum frequency generation spectroscopy. The electronic resonance associated with the stretching mode of atop CO appeared at 2.51 eV with a bandwidth of 0.83 eV. The result is consistent with earlier calculations using CO-Pt cluster models indicating that the resonance is from $5d$ to $6sp$ orbital of Pt hybridized with orbital of CO. The measured transition energy suggests that the antibonding state of Pt $6sp$ and CO $5\ensuremath{\sigma}$ for atop CO on Pt(111) is $\ensuremath{\sim}2.2\mathrm{eV}$ above Fermi level.

Infrared-visible sum frequency generation investigation of Cu corrosion inhibition with benzotriazole.

Infrared-visible sum frequency generation spectroscopy is used to investigate the corrosion inhibitor benzotriazole (BTAH) adsorbed on Cu(100) and Cu(111) in acidic solution. Potential-dependent in situ spectra indicate that the adsorbed molecule is the benzotriazole anion (BTA-) at all potentials investigated. The Cu(100) surface is shown to form an ordered adlayer at all potentials probed, while the Cu(111) face is shown to be disordered at negative potentials, but to order with applied positive potential. The ordered adlayer is shown to consist of the BTA- in two configurations, one coordinated to the surface and Cu+ ions in solution and the other coordinated only to the surface. The BTA- coordinated to Cu+ is shown to be more stable with respect to Cl- addition than BTA- coordinated to only the surface. This study demonstrates the viability of using sum frequency generation to study corrosion inhibition in situ.

Effect of a static electric field on the vibrational and electronic properties of a compressed CO adlayer on Pt(110) in nonaqueous electrolyte as probed by infrared reflection–absorption spectroscopy and infrared-visible sum-frequency generation spectroscopy

The CO–Pt(110) in nonaqueous electrolyte electrochemical interface was studied by infrared reflection–absorption spectroscopy (IRAS) and infrared (IR)-visible sum-frequency generation (SFG) nonlinear vibrational spectroscopy over a wide range of applied potentials (−1.7⩽Φ⩽1 V/NHE). The integrated intensities of the IRAS and SFG peaks associated with resonant excitation of the atop CO internal stretch vibration (AIR and ASFG) showed distinct variations with Φ. The influence of vibrational and electronic properties on the observed variations is discussed. Potential dependent dynamical charge transfer is not sufficient to explain the observed value of ∂AIR/∂Φ. It is shown that screening factors due to dipolar interactions between molecules within the compressed adsorbed layer must be taken into account in order to explain the variations of the IRAS and SFG data and that the observed behavior differences of AIR and ASFG with the potential are not necessarily related to changes in the Raman cross section of the adsorbate.

Infrared-Visible Sum Frequency Generation Spectroscopic Study of Molecular Orientation at Polystyrene/Comb-Polymer Interfaces

Surface-sensitive infrared-visible sum frequency generation spectroscopy (SFG) in total internal reflection geometry has been used to study the structure of poly(vinyl n-octadecyl carbamate-co-vinyl acetate) (PVNODC) or poly(octadecyl acrylate) (PA-18) in contact with a deuterated or hydrogenated polystyrene (dPS or hPS) layer. SFG spectra from the PVNODC (or PA-18)/hPS interface show methyl and methylene peaks corresponding to PVNODC (or PA-18) and phenyl peaks corresponding to the PS. Analysis suggests that the methyl groups are tilted at angles less than 30 degrees with respect to the surface normal. The presence of a strong methylene peak suggests the PVNODC alkyl side chains contain more gauche defects at the PS/PVNODC interface in comparison to PVNODC (or PA-18)/air interfaces. On heating, the SFG intensity from the PS/PA-18 interface drops sharply near the bulk melting temperature (T(m)) of PA-18. Interestingly, a similar drop in SFG signal is also observed for the PS phenyl groups. This demonstrates the ability of the phenyl group at the PS/PA-18 interface to rearrange itself upon the solid-to-liquid transition of the PA-18 alkyl side chain, at a temperature well below the bulk PS glass transition temperature. For PS/PVNODC interfaces, the drop in SFG intensity is gradual and in agreement with the three broad transitions of PVNODC observed in the bulk.