Phase-sensitive Sum Frequency Generation Research Articles

Absolute local conformation of poly(methyl methacrylate) chains adsorbed on a quartz surface.

Polymer chains at a buried interface with an inorganic solid play a critical role in the performance of polymer nanocomposites and adhesives. Sum frequency generation (SFG) vibrational spectroscopy with a sub-nanometer depth resolution provides valuable information regarding the orientation angle of functional groups at interfaces. However, in the case of conventional SFG, since the signal intensity is proportional to the square of the second-order nonlinear optical susceptibility and thereby loses phase information, it cannot be unambiguously determined whether the functional groups face upward or downward. This problem can be solved by phase-sensitive SFG (ps-SFG). We here applied ps-SFG to poly(methyl methacrylate) (PMMA) chains in direct contact with a quartz surface, shedding light on the local conformation of chains adsorbed onto the solid surface. The measurements made it possible to determine the absolute orientation of the ester methyl groups of PMMA, which were oriented toward the quartz interface. Combining ps-SFG with all-atomistic molecular dynamics simulation, the distribution of the local conformation and the driving force are also discussed.

Absolute molecular structure of the polystyrene at the buried polystyrene/silica interface and its relationship to dewetting during annealing

Dewetting is a common phenomenon observed from polymer thin films under stimuli, such as annealing, which directly affects the applications of polymer thin films. A key to understanding such dewetting behavior is to precisely probe the molecular structure evolution at the buried polymer/substrate interface during annealing. However, non-destructively probing the buried interface is very difficult at the molecular level and in situ. In this study, the specific surface- and phase-sensitive sum frequency generation (SFG) vibrational spectroscopy was used to investigate PS thin films on silica substrates during annealing. The results showed that the absolute orientation/conformation of PS at the film surface was significantly different from that of the flattened PS nanolayer formed near the substrate by dewetting. The dynamic molecular structure evolution of the PS nanolayer (the formation process of the flattened PS nanolayer) at the buried PS/silica interface was directly observed in situ. The dewetting occurred at the non-adsorbed (bulk, free) PS/the flattened PS nanolayer interface due to the autophobic effect. Furthermore, the effects of end groups and solvents on the PS dewetting rate were also elucidated. This study provides a molecular-level understanding of the PS structure at the buried PS/silica interface and its relationship to dewetting behavior.

Elucidating molecular mechanisms of two-dimensional chemical reactions

Elucidating molecular mechanisms of two-dimensional chemical reactions

Role of Ions on the Surface-Bound Water Structure at the Silica/Water Interface: Identifying the Spectral Signature of Stability.

Isolating the hydrogen-bonding structure of water immediately at the surface is challenging, even with surface-specific techniques like sum-frequency generation (SFG), because of the presence of aligned water further away in the diffuse layer. Here, we combine zeta potential and SFG intensity measurements with the maximum entropy method referenced to reported phase-sensitive SFG and second-harmonic generation results to deconvolute the SFG spectral contributions of the surface waters from those in the diffuse layer. Deconvolution reveals that at very low ionic strength, the surface water structure is similar to that of a neutral silica surface near the point-of-zero-charge with waters in different hydrogen-bonding environments oriented in opposite directions. This similarity suggests that the known metastability of silica colloids against aggregation under both conditions could arise from this distinct surface water structure. Upon the addition of salt, significant restructuring of water is observed, leading to a net decrease in order at the surface.

Progress in phase-sensitive sum frequency generation spectroscopy.

Sum frequency generation (SFG) spectroscopy is a unique and powerful tool for investigating surfaces and interfaces at the molecular level. Phase-sensitive SFG (PS-SFG) is an upgraded technique that can overcome the inherent drawbacks of conventional SFG. Here we review several methods of PS-SFG developed and reported in 1990-2020. We introduce how and by which group each PS-SFG method was designed and built in terms of interferometer implementation for optical heterodyne detection, with one exception of a recent numerical method that does not rely on interferometry. We also discuss how PS-SFG solved some typical problems for aqueous interfaces that were once left open by conventional SFG. These problems and their solutions are good examples to demonstrate why PS-SFG is essential. In addition, we briefly note a few terminology issues related with PS-SFG to avoid confusion.

High-resolution phase-sensitive sum frequency generation spectroscopy by time-domain ptychography

We demonstrate that time-domain ptychography, when applied to a set of broadband vibrational sum frequency spectra, reconstructs amplitude and phase of the vibrational free induction decay from an interfacial sample with a resolution that is independent of up-converting pulse bandwidth and spectrometer resolution. These important improvements require no modifications to most standard homodyne setups, and the method is applicable to other coherent homodyne spectroscopies such as coherent anti-Stokes Raman spectroscopy and transient grating spectroscopy.

Quantitative determination of the nonlinear bulk and surface response from alpha-quartz using phase sensitive SFG spectroscopy

We investigate the nonlinear optical response of alpha-quartz with phase-sensitive vibrational sum frequency generation (SFG) spectroscopy. Phase and amplitude of the generated sum frequency signal are determined by a complex interplay between signal contributions from the surface and the bulk of the crystal with the experimental geometry, in particular, the quartz azimuth. By combining anisotropy measurements with spectral- and phase resolution in our SFG experiment, we study this interplay and show that we can quantitatively isolate and characterize the contributions from the surface and bulk of the crystal. The obtained optical constants in combination with the presented mathematical framework fully describe the nonlinear response and allow for a precise determination of the phase of the overall SFG signal of quartz for any experimental geometry. This knowledge is of particular relevance because quartz is commonly used as a reference in phase sensitive SFG experiments. In such studies, the surface contribution is typically neglected and a constant value for the phase of the sum frequency response is assumed. Our study shows that this assumption is not generally accurate by revealing the considerable impact that the surface contribution can have on the overall response of the crystal.

Measurements indicate alpha-quartz’s surface signal should not be neglected in spectroscopy calibration

Phase-sensitive sum frequency generation spectroscopy reveals that the contribution from the surface of alpha-quartz to the overall sum frequency response signal is more significant than previously assumed.

Absolute Orientations of Water Molecules at Zwitterionic Polymer Interfaces and Interfacial Dynamics after Salt Exposure.

Nonfouling zwitterionic polymers have wide applications ranging from the naval industry to biomedical engineering. Strong hydration at polymer surfaces has been proven to be crucial to their nonfouling property, but the absolute orientations of water molecules on the polymers and the competition between water and salt binding have not been elucidated. In this work, the absolute orientations of water molecules on two zwitterionic polymer brushes, poly(carboxybetaine methacrylate) (pCBMA) and poly(sulfobetaine methacrylate) (pSBMA), were measured using regular and phase-sensitive sum frequency generation (SFG) vibrational spectroscopy. The pH-dependent studies in a pH range from 2 to 12 showed that at a pH of 7, the water absolute orientations are different on the pCBMS and pSBMA surfaces. Phase-sensitive SFG studies confirmed the results obtained from the pH-dependent measurements. Salt effects on the hydration of zwitterionic polymers were examined as a function of time, which indicated that the pCBMA surface and the associated interfacial water exhibit a slow restructuring process after salt binding (likely due to the strong binding of pCBMA with water), whereas the surface of pSBMA and the associated water have a fast change after salt binding.

Nonlinear interferometer: Design, implementation, and phase-sensitive sum frequency measurement.

Sum frequency generation (SFG) spectroscopy is a unique tool for probing the vibrational structure of numerous interfaces. Since SFG is a nonlinear spectroscopy, it has long been recognized that measuring only the intensity-the absolute square of the surface response-limits the potential of SFG for examining interfacial interactions and dynamics. The potential is unlocked by measuring the phase-sensitive or imaginary response. As with any phase, the phase-sensitive SFG response is measured relative to a reference; the spatial relationship between the phase reference and the sample modulates the observed interference intensity and impacts sensitivity and accuracy. We have designed and implemented a nonlinear interferometer to directly measure the phase-sensitive response. If the phase of the reference is known, then the interferometer produces an absolute phase of the surface. Compared to current configurations, phase accuracy and stability are greatly improved due to active stabilization of the sample-reference position. The design is versatile and thus can be used for any system that can be probed with SFG including buried interfaces and those with high vapor pressure. Feasibility and advantages of the interferometer are demonstrated using an octadecyltrichlorosilane film on fused silica.

Chemisorbed and Physisorbed Water at the TiO2/Water Interface.

The interfacial structure of water in contact with TiO2 is the key to understand the mechanism of photocatalytic water dissociation as well as photoinduced superhydrophilicity. We investigate the interfacial molecular structure of water at the surface of anatase TiO2, using phase-sensitive sum frequency generation spectroscopy together with spectra simulation using ab initio molecular dynamic trajectories. We identify two oppositely oriented, weakly and strongly hydrogen-bonded subensembles of O–H groups at the superhydrophilic UV irradiated TiO2 surface. The water molecules with weakly hydrogen-bonded O–H groups are chemisorbed, i.e. form hydroxyl groups, at the TiO2 surface with their hydrogen atoms pointing toward bulk water. The strongly hydrogen-bonded O–H groups interact with the oxygen atom of the chemisorbed water. Their hydrogen atoms point toward the TiO2. This strong interaction between physisorbed and chemisorbed water molecules causes superhydrophilicity.

Revisiting the Thermodynamics of Water Surfaces and the Effects of Surfactant Head Group.

It is common knowledge that surfactants lower the surface tension of water. The typical textbook explanation of this phenomenon is that the force of attraction between surfactant and water molecules is less than that between two water molecules; hence the surface contraction force decreases in the presence of surfactants; however, this common description, based on the strength of intermolecular interactions, is overly simplified because it ignores an important thermodynamic function: the surface entropy of water. Here we report separate measurements of water's surface enthalpy and surface entropy in the presence of nonionic, zwitterionic, anionic, and cationic surfactants. While all of these surfactants decreased the surface enthalpy of water by 50-70%, the surface entropy of water could drop to near-zero or even negative values for ionic surfactants. Studies of this zero-entropy state of water surface using phase-sensitive sum-frequency generation (SFG) vibrational spectroscopy and molecular dynamics (MD) simulations suggested that the zero-entropy state of the water surface was associated with surfactant-induced ordering of water molecules and enhanced hydrogen bond formation at the water surface. Both effects reduce water molecules' degrees of freedom for motion and thus lower the surface entropy of water. The ability of a surfactant to decrease the surface entropy of water is in the order ionic > zwitterionic > nonionic. For all surfactant head groups surface entropy plays a critical role in determining the surface tension of water. The description of water's surface tension is not complete without considering its surface entropy.

Surface Charge at the Bitumen/Water Interface Investigated by Phase-Sensitive Sum Frequency Generation Vibrational Spectroscopy: Effects of pH, Ions, and Surfactants

The structure of water at bitumen/water interfaces was studied using phase-sensitive sum frequency generation (SFG) vibrational spectroscopy. The sign of the SFG spectra indicated that the surface of bitumen has a negative net charge. An ordered water structure was observed on the bitumen surface, and the ordering was enhanced at the industry-relevant pH value of 9. The presence of salt in the water neutralized the surface charge of bitumen and nearly destroyed the ordered water structure with a concentration of ∼100 mM. It was found that Ca2+ was more effective than Na+ in screening the surface charge of bitumen. Both the anionic surfactant sodium dodecyl sulfate (SDS) and the cationic surfactant dodecyl trimethylammonium chloride (DTAC) interacted with the bitumen. While the anionic surfactant slightly increased the negative charge of the bitumen surface, the cationic surfactant produced a surface charge reversal, indicated by the sign change of the SFG spectrum.

Interactions of water with the nonionic surfactant polyoxyethylene glycol alkyl ethers studied by phase-sensitive sum frequency generation and molecular dynamics simulation

Phase-sensitive sum frequency generation (SFG) vibrational spectroscopy and molecular dynamics (MD) simulation were used to study the interactions between water molecules and the surfactant polyoxyethylene glycol alkyl ether (C12E4) at its critical micelle concentration. The surfactant enhanced the positive peak of water's SFG spectrum suggesting that C12E4 was more anionic-like, even though the surfactant was overall neutral. MD simulations showed that the surfactant increased the depth of the surface anisotropic layer from 0.31 to 1.82nm and the average number of hydrogen bonds per water molecule from 2.7 to 3.1. For water molecules near the surfactant, their H and O atoms are confined in well-separated shells. Both the O and C atoms in the head group of the surfactant are surrounded by the H atoms, instead of the O atoms, of water indicating that the negatively charged O atoms of the surfactant play a more important role than the C atoms in determining the orientation of water. The simulation also showed that the orientation of surface water molecules was flipped in the presence of the surfactant, which was consistent with the observed SFG spectra.

Retrieval of complex χ((2)) parts for quantitative analysis of sum-frequency generation intensity spectra.

Vibrational sum-frequency generation (SFG) spectroscopy has become an established technique for in situ surface analysis. While spectral recording procedures and hardware have been optimized, unique data analysis routines have yet to be established. The SFG intensity is related to probing geometries and properties of the system under investigation such as the absolute square of the second-order susceptibility χ((2)) (2). A conventional SFG intensity measurement does not grant access to the complex parts of χ((2)) unless further assumptions have been made. It is therefore difficult, sometimes impossible, to establish a unique fitting solution for SFG intensity spectra. Recently, interferometric phase-sensitive SFG or heterodyne detection methods have been introduced to measure real and imaginary parts of χ((2)) experimentally. Here, we demonstrate that iterative phase-matching between complex spectra retrieved from maximum entropy method analysis and fitting of intensity SFG spectra (iMEMfit) leads to a unique solution for the complex parts of χ((2)) and enables quantitative analysis of SFG intensity spectra. A comparison between complex parts retrieved by iMEMfit applied to intensity spectra and phase sensitive experimental data shows excellent agreement between the two methods.

Molecular Dynamics Analysis of NaOH Aqueous Solution Surface and the Sum Frequency Generation Spectra: Is Surface OH– Detected by SFG Spectroscopy?

We elucidated the phase-sensitive sum frequency generation (SFG) spectrum of NaOH aqueous solution by molecular dynamics simulation. The MD analysis reproduced the effects of NaOH on the imaginary χ(2) spectrum, characterized with a positive (upward) shift in the amplitude in midfrequency region (3300–3600 cm–1) and a negative (downward) shift in low frequency (3000–3200 cm–1). We found that the positive shift is a consequence of electric double layers, while the negative shift is attributed to the first solvation shell of OH–. The latter mechanism generally holds for electrolyte solutions, though it becomes conspicuous for the NaOH solution in the low-frequency tail region. These perturbation mechanisms evidence that OH– at the surface is fully hydrated and not preferentially exposed to the surface.

Interactions of Polyelectrolytes with Water and Ions at Air/Water Interfaces Studied by Phase-Sensitive Sum Frequency Generation Vibrational Spectroscopy

Interactions of the polyelectrolyte partially hydrolyzed polyacrylamide (HPAM) with water and cations at air/liquid interfaces were studied using phase-sensitive sum frequency generation (SFG) vibrational spectroscopy. In contrast to the conventional SFG vibrational spectroscopy which measures only the amplitude of the second-order susceptibility |χ(2)|, the heterodyne-detected SFG measures the complex χ(2) which contains information about the absolute orientation of surface molecules. While the OH groups of water near a neat air/water interface mostly pointed down to the bulk (downward), the presence of the polyelectrolyte caused flipping of water molecules with the hydrogen being oriented upward. With 10–7 M HPAM, water showed a highly ordered structure with a single peak near 3100 cm–1, but higher concentrations resulted in a less ordered water structure with multiple peaks. The addition of the monovalent cation Na+ to the polyelectrolyte solution did not affect the conformation of the polyelectrolyte, though the water molecules flipped back to a structure similar to that of a neat air/water interface with the hydrogen pointing down. On the other hand, the addition of divalent cation Ca2+ not only changed the conformation of the polyelectrolyte but also completely destroyed the ordered structure of interfacial water molecules. The observed phenomena support the polymer–ion complex model in which a divalent cation can interact with two intrachain or interchain charges and form a jointing point. The amorphous nature of the polymer–ion complex explained the disappearance of the ordered water structure in the presence of divalent cations.

Organization of Water and Atmospherically Relevant Ions and Solutes: Vibrational Sum Frequency Spectroscopy at the Vapor/Liquid and Liquid/Solid Interfaces

The nature of water's hydrogen-bonding network is a vital influence on the chemistry that occurs at interfaces, but a complete understanding of interfacial water has proven elusive. Even-order nonlinear optical spectroscopies, such as vibrational sum frequency generation (VSFG) spectroscopy and heterodyne detected phase-sensitive sum frequency generation (PS-SFG) spectroscopy, are inherently surface specific. With the advent of advances in these spectroscopic techniques, researchers can now explore many long-standing questions about the dynamics and structures present at the vapor-water and water-solid interfaces. Of special interest to the atmospheric chemistry community is the accommodation of ions and solutes by water's hydrogen-bonding network. A better understanding of how ions and solutes behave in hydrogen-bonded water has afforded a fresh perspective of aqueous aerosols, because the interactions involved therein drive phenomena such as the hydrolysis of atmospheric chemical species. In this Account, we present work from our laboratory focusing on applying VSFG and the recently developed PS-SFG techniques to probe the perturbation of water's hydrogen-bonding network at the vapor-water interface by a variety of ions and solutes. We also present very recent results from our laboratory on the direct observation of the adsorption of ions at the water-CaF(2) interface. We begin by discussing the influence of ions and solutes on interfacial water structure. Results for halide salts and the acid analogs on interfacial water structure are shown to be quite different, as would be expected from differences in surface tension measurements that have been known for a long time. Also examined are systems with the largely polarizable molecular anions nitrate (NO(3)(-)), sulfate (SO(4)(2-)), carbonate (CO(3)(2-)), and bicarbonate (HCO(3)(-)).These systems feature more complicated influences on interfacial water structure than halide-containing solutions; however, our conventional VSFG results for both nitrate and sulfate solutions are in agreement with recent PS-SFG results and molecular dynamics simulations. We also discuss recent PS-SFG work on carbonate and bicarbonate systems in which the accommodation of the bicarbonate ion at the vapor-water interface is in stark contrast to the carbonate results. Perturbation of interfacial water by solutes is examined for solutions of dimethyl sulfoxide and methylsulfonic acid. PS-SFG results for these systems are striking: they illustrate the dramatic changes that interfacial water molecules undergo in the presence of solutes that are not observed with conventional VSFG. Finally, we discuss direct sulfate ion adsorption for the aqueous sodium sulfate-CaF(2) interface, with the goal of elucidating water behavior at this surface.

Electric Field Reversal of Na2SO4, (NH4)2SO4, and Na2CO3 Relative to CaCl2 and NaCl at the Air/Aqueous Interface Revealed by Heterodyne Detected Phase-Sensitive Sum Frequency

Phase-sensitive sum frequency generation (PS-SFG) spectroscopy, heterodyne detected, was used to investigate the average direction of the transition dipole moment of interfacial water molecules that is intrinsically contained in the sign of the second-order nonlinear susceptibility, χ(2). The organization of water at air/aqueous inorganic salts interfaces of CaCl2, NaCl, Na2SO4, (NH4)2SO4, and Na2CO3 was inferred. We attribute our findings to the net charge separation arising from the ion distributions at the air/water interface assuming similar ion distribution widths for all systems studied. This is most evident for the aqueous ammonium sulfate solution where the electric field has a greater magnitude relative to the other salt solutions studied. The magnitude of the electric field in the interfacial region decreases in the order (NH4)2SO4 > Na2SO4 > Na2CO3 ≥ CaCl2 > NaCl; the electric field is opposite in direction for the sulfate and carbonate salts relative to the chloride salts.

Phase-Sensitive Sum Frequency Revealing Accommodation of Bicarbonate Ions, and Charge Separation of Sodium and Carbonate Ions within the Air/Water Interface

Interfacial water structure plays a key role in many chemical, biological, and environmental processes. Here, in addition to conventional VSFG, we employ phase-sensitive sum frequency generation (PS-SFG) to investigate the average direction of the transition dipole of interfacial water molecules that is intrinsically contained in the sign of the second-order nonlinear susceptibility, χ((2)). The orientation of water at air/aqueous inorganic salt interfaces of Na(2)CO(3) and NaHCO(3) was inferred from the direct measurement of the transition dipole moment of the interfacial water molecules. It is found that bicarbonate and its counterion sodium do not significantly perturb the interfacial water structure, whereas carbonate strongly orients water so that the water hydrogens point down toward the bulk solution. This is consistent with the picture of carbonate anions residing many layers below the water surface with a preference for the sodium cations to be above the anions and thereby closer to the topmost layer of the water surface.