Sum Frequency Generation Surface Research Articles

Ultrafast Spectroscopy at the Central Laser Facility

In this article, we will examine ultrafast spectroscopy techniques and applications, covering time-resolved infrared (TR-IR) spectroscopy, time resolved visible (TA) spectroscopy, two-dimensional infrared (2D-IR) spectroscopy, Kerr-gated Raman spectroscopy, time-resolved Raman and surface sum-frequency generation (SSFG) spectroscopy. In addition to introducing each technique, we will cover some basics, such as what kinds of lasers are used and discuss how these techniques are applied to study a diversity of chemical problems such as photocatalysis, photochemistry, electrocatalysis, battery electrode characterisation, zeolite characterisation and protein structural dynamics.

Observation of a Two-Dimensional Hydrophobic Collapse at the Surface of Water Using Heterodyne-Detected Surface Sum-Frequency Generation.

We study the effect of sodium chloride (NaCl) on the properties of the interface of water and the surfactant dodecyl sulfate (DS-) using heterodyne-detected vibrational sum-frequency generation spectroscopy. We find that the signal of the O-H stretch vibrations of oriented water molecules at the interface is highly nonlinearly dependent on the NaCl concentration. This nonlinear dependence is explained by a combination of screening of the electric field of surface-bound DS- ions pointing into the bulk and screening of the Coulomb repulsion between the headgroups of the DS- ions in the surface plane. The latter effect strongly increases the oriented water signal within a limited NaCl concentration range of 10-100 mM, indicating a two-dimensional hydrophobic collapse of the surfactant layer. The occurrence of collapse is supported by model calculations of the surface potential and surface surfactant density.

Elucidating the Molecular Structure of Hydrophobically Modified Polyethylenimine Nanoparticles and Its Potential Implications for DNA Binding.

The structural properties of the polyethylenimine (PEI) polymer are generally tuned and selectively modified to reinforce its potential in a broad spectrum of applied domains of medicine, healthcare, material design, sensing, and electronic optimization. The selective modification of the polymer brings about changes in its interfacial characteristics and behavior. The current work involves the synthesis of naphthalimide conjugated polyethylenimine organic nanoparticles (NPEI-ONPs). The interfacial molecular structure of NPEI-ONPs is explored in an aqueous medium at pH 7.4 using surface tensiometry and sum-frequency generation vibrational spectroscopy (SFG-VS). The hydrophobic functionalization rendered a concentration-dependent surface coverage of NPEI-ONPs, where the SFG-VS analysis exhibited the molecular rearrangement of its hydrophobic groups at the interface. The interaction of NPEI-ONPs with double-stranded DNA (dsDNA) is carried out to observe the relevance of the synthesized nanocomposites in the biomedical domain. The bulk-specific studies (i.e., thermal denaturation, viscometry, zeta (ζ) potential, and ATR-FTIR) reveal the condensation of dsDNA in the presence of NPEI-ONPs, making its structure more compact. The interface-sensitive SFG-VS showcased the impact of the dsDNA and NPEI-ONP interaction on the interfacial molecular behavior of NPEI-ONPs at the air-aqueous interface. Our results exhibit the potential of such hydrophobically functionalized ONPs as promising candidates for developing biomedical sealants, substrate coatings, and other biomedical domains.

Surface sum-frequency generation from chiral medium by elliptically polarized light beyond plane-wave approximation and coplanar geometry of incidence

Aiming to study the nonlinear response of the surface of isotropic chiral medium, we obtained analytical expression relating the transverse amplitudes of the spatial Fourier-spectra of two incident arbitrary polarized fundamental beams and one signal reflected beam at the sum-frequency within the first-order approximation by their divergence angles. The calculations, carried out in paraxial approximation, simultaneously take into account the spatial dispersion of the bulk of the medium, its near-surface heterogeneity and the transverse finiteness of the three interacting light beams with arbitrary amplitude profiles and orientation in space. A special compact form for the final formulas was found, which makes use of effective nonlinear transformation tensors, the components of which are solely determined by the geometry of incidence of the beams and the material constants of the medium. A possibility of ‘switching off’ the certain mechanisms of nonlinear response by choosing the specific polarization states of the incident beams is discussed.

Bulk Response of Carboxylic Acid Solutions Observed with Surface Sum-Frequency Generation Spectroscopy.

We study the molecular properties of aqueous acetic acid and formic acid solutions with heterodyne-detected vibrational sum-frequency generation spectroscopy (HD-VSFG). For acid concentrations up to ∼5 M, we observe a strong increase of the responses of the acid hydroxyl and carbonyl stretch vibrations with increasing acid concentration due to an increase of the surface coverage by the acid molecules. At acid concentrations >5 M we observe first a saturation of these responses and then a decrease. For pure carboxylic acids we even observe a change of sign of the Im[χ(2)] response of the carbonyl vibration. The decrease of the response of the hydroxyl vibration and the decrease and sign change of the response of the carbonyl vibration indicate the formation of cyclic dimers, which only show a quadrupolar bulk response in the HD-VSFG spectrum because of their antiparallel conformation. We also find evidence for the presence of a quadrupolar response of the CH vibrations of the acid molecules.

Efficient generation of narrowband picosecond pulses from a femtosecond laser.

In some applications of broadband ultrafast spectroscopy, such as surface sum frequency generation vibrational spectroscopy, femtosecond stimulated Raman spectroscopy (SRS), and coherent anti-Stokes Raman spectroscopy, a narrowband picosecond pulse is required to obtain a high spectral resolution. Here, we present a method to generate narrowband picosecond second harmonic (SH) and fundamental frequency (FF) pulses with high-conversion efficiency from a Ti:sapphire femtosecond laser amplifier. The narrowband picosecond SH pulse was generated based on the group velocity mismatch between the SH and FF pulses in a nonlinear crystal of β-barium borate (BBO). The small SH nonlinear optical coefficient was optimized by changing the azimuth angle of a thick BBO crystal, successfully avoiding the saturation effect in the SH generation process. The SH pulse was then used to pump an optical parametric amplifier to efficiently amplify the narrowband FF seed pulse, which was obtained with an etalon by spectrally filtering the output from the femtosecond laser amplifier. Dual-wavelength output, which could be very useful in femtosecond SRS, was also realized.

Chemical Imaging of Surfaces with Sum Frequency Generation Vibrational Spectroscopy.

Surface chemistry is a key area of study in the chemical sciences, and many system properties are dominated by the chemistry at the interface between two bulk media. While the interface may have a large influence on the system behavior, there are relatively few molecules at the interface compared to the bulk; thus, probing their unique properties has become a specialized field in physical chemistry. In addition to the heterogeneous phase chemistry, surfaces also present spatial heterogeneity (Chemistry in Two Dimensions). This 2D chemistry affects the properties as much as the heterogeneous phases. If we consider the Cartesian z-axis as defining the dimension across the interface between the two bulk phases, then the x-y plane is the 2D region of the surface. We might even consider that the majority of surface chemistry has been concerned with this z-dimension, i.e., surface structure, partition excess, thermodynamics, etc. relative to the bulk, where the 2D distribution was only considered on average. This treatment is understandable since few techniques provide the spatial and chemical resolution needed to deduce the effects of 2D heterogeneity on the surface properties. It is desirable to use an all-optical technique for interface studies because the optical methods provide the chemical specificity through spectroscopy. Also, the use of second-order spectroscopy is typically surface-sensitive without background subtractions or enhancement mechanisms that could limit the range of systems to be investigated.In this Account, the development and selected results of sum frequency generation microscopy and its contributions to the surface chemistry are presented. Sum frequency generation (SFG) provides a unique probe for studying surface chemistry in ambient conditions with surface specificity. SFG provides image contrast based on multiple-chemically important-mechanisms such as chemical functional groups, molecular orientation, surface concentration, molecular conformation, local electric fields, among others. To understand the spatial distribution of heterogeneous chemistry, multiple microscopy methods have been developed which utilize the SFG process to yield spatial information with chemical sensitivity. These spectroscopic-microscopies come with unique advantages as well as challenges. Multiple solutions have been developed in this field to overcome the challenges and improve the advantages. In this Account, some of the leading SFG surface microscopies for surface studies are introduced. Initially, direct imaging of the SFG signal onto a CCD camera provided spatially and spectrally resolved imaging of monolayers on surfaces. However, to speed up the imaging process, the technique of compressive sensing was applied to SFG imaging. Most recently the use of machine learning methods and target factor analysis have improved the quality and acquisition speed of SFG images.

Investigating the interactions of corona-free SWCNTs and cell membrane models using sum-frequency generation.

The understanding of the interactions between biomolecules and nanomaterials is of great importance in many areas of nanomedicine and bioapplications. Numerous studies in this area have been performed. However, toxicological aspects involving the interaction between phospholipids and carbon nanotubes (CNTs) remain undefined, especially for those cases in which a protein corona is not formed around the nanomaterial (corona-free nanomaterials). This study focuses on the interaction of Langmuir films of dipalmitoylphosphatidylglycerol (DPPG) and dipalmitoylphosphatidylcholine (DPPC) with corona-free, single-walled CNTs. Surface pressure-area isotherms and sum-frequency generation (SFG) vibrational spectroscopy, a non-linear optical technique used to study surfaces and interfaces, were used to investigate the lipid tail orientation and conformation, aiming to understand the interactions between phospholipids and single walled carbon nanotubes functionalized by carboxylic acid (SWCNTs-COOH) at the air-water interface under low ionic strength conditions. Data from isotherms and SFG spectra revealed that the SWCNT adsorption at the air-water interface is induced by the presence of both lipids, although at a lesser extent for DPPG due to its anionic head group, which could result in repulsion of SWCNTs-COOH that also bear a negative charge. Furthermore, lipid monolayers remained conformationally ordered, indicating insertion of SWCNTs into the lipid monolayer. Our results corroborate previous works and simulations in the literature, but made it possible to perform an in-depth investigation of the interaction of these nanomaterials with components of phospholipid membranes.

Active Species in Photocatalytic Reactions of Methanol on TiO2(110) Identified by Surface Sum Frequency Generation Vibrational Spectroscopy

The photocatalytic reactivity of one monolayer of methanol on TiO2(110) was measured with the surface sum frequency generation vibrational spectroscopy in the C-H stretching range, which shows high photon energy dependence. The photocatalytic reactivity was systematically investigated for different active species on TiO2(110), dissociative adsorbed methanol at five-coordinated Ti sites (Ti-5c), methoxy without adsorbed methanol at Ti-5c sites, and methoxy O-b sites. The results show that the methoxy at Ti-5c sites has much higher photocatalytic reactivity than that of dissociative adsorbed methanol at Ti-5c sites, and the methoxy at O-b sites might be inactive. This work demonstrates that methoxy at Ti-5c sites is the most active species on TiO2(110) and suggests that effectively removing surface OH could enhance the photodegradation of surface organics.

In Situ Studies on Temperature-Dependent Photocatalytic Reactions of Methanol on TiO2(110)

We studied the photocatalytic reaction of methanol on the TiO2(110) surface in situ by surface sum frequency generation vibrational spectroscopy. The in situ vibrational spectra of the photo-oxidat...

Powder sum-frequency generation as a versatile method for infrared optical alignment

The sum-frequency generation (SFG) in potassium dihydrogen phosphate (KDP) powder with μm-grade particle size is successfully demonstrated under various experimental conditions. Two focused beams of 870 nm and 1369 nm are used for SFG excitation. SFG is observed under different excitation energies. The SFG intensity shows isotropy with different observation azimuths. The intersection angle between two excitation beams is not limited by conventional phase-matching conditions, and it owns the flexibility of a very large allowed range, e.g., it can be 0°∼100° in this work. The polarization combination of excitation beams is not limited either. Thanks to the non-toxicity, low price, and low SFG threshold properties of KDP material and the optical flexibility, this powder SFG technology is a versatile method and is expected to be applied to various situations of optical alignment, e.g., surface SFG, four-wave mixing, coherent anti-Stokes Raman spectroscopy, multi-color laser excitation, etc. The effect of potential powder SFG-assisted optical alignments is also discussed. Extension of this method to multi-beams, tight focusing beams, and plasmonic polariton devices is proposed.

Methanol Adsorption on TiO2 Film Studied by Sum Frequency Generation Vibrational Spectroscopy

A broadband infrared surface sum frequency generation vibrational spectroscopy (SFG-VS) and an in situ UV excitation setup devoted to studying surface photocatalysis have been constructed. With a home-made compact high vacuum cell, organic contaminants on TiO2 thin film surface prepared by RF magnetron sputtering were in situ removed under 266 nm irradiation in 10 kPa O2 atmosphere. We obtained the methanol spectrum in the CH3 stretching vibration region on TiO2 surface with changing the methanol pressure at room temperature. Features of both molecular and dissociative methanol, methoxy, adsorbed on this surface were resolved. The CH3 symmetric stretching vibration frequency and Fermi resonance of molecular methanol is red-shifted by about 6–8 cm−1 from low to high coverage. Moreover, the recombination of dissociative methanol and H on surfaces in vacuum was also observed. Our results suggest two equilibria exist: between molecular methanol in the gas phase and that on surfaces, and between molecular methanol and dissociative methanol on surfaces.

Gigahertz Modulation of Femtosecond Time-Resolved Surface Sum-Frequency Generation Due to Acoustic Strain Pulses

We study the properties of aqueous solution/air interfaces with time-resolved surface sum-frequency generation (SFG) spectroscopy. Using this technique, we monitor the change in SFG signal following the excitation of the water hydroxyl stretch vibrations with a strong ultrashort infrared pump pulse. We observe that, in addition to the excitation-induced changes in the signal resulting from vibrational excitation and relaxation on a time scale of picoseconds, the infrared excitation also induces a modulation of the SFG signal with a period of ∼180 ps. This modulation is caused by the interference between the SFG field directly radiated away from the air/liquid interface and the SFG field reflected or generated at the acoustic strain wavefront that is created by the infrared excitation pulse. The modulation is observed to be much stronger for aqueous salt solutions than for pure water, and the phase of the oscillations depends on the nature of the dissolved salt. This dependence of the phase can be explained from the differences in surface propensities of the ions of the different salts, giving rise to different net orientation of the interfacial water species.

Towards the identification of molecular constituents associated with the surfaces of isoprene-derived secondary organic aerosol (SOA) particles

Abstract. Secondary organic aerosol (SOA) particle formation ranks among the least understood chemical processes in the atmosphere, rooted in part in the lack of knowledge about chemical composition and structure at the particle surface, and little availability of reference compounds needed for benchmarking and chemical identification in pure and homogenous form. Here, we synthesize and characterize SOA particle constituents consisting of the isoprene oxidation products α-, δ-, and cis- and trans-β-IEPOX (isoprene epoxide), as well as syn- and anti-2-methyltetraol. Paying particular attention to their phase state (condensed vs. vapor), we carry out a surface-specific and orientationally selective chemical analysis by vibrational sum frequency generation (SFG) spectroscopy of these compounds in contact with a fused silica window. Comparison to the vibrational SFG spectra of synthetic isoprene-derived SOA particle material prepared at the Harvard Environmental Chamber yields a plausible match with trans-β-IEPOX, suggesting it is an abundant species on their surfaces, while the other species studied here, if present, appear to be SFG inactive and thus likely to be localized in a centrosymmetric environment, e.g., the particle bulk. No match is found for authentic SOA particle material collected at the site of the Amazonian Aerosol Characterization Experiment (AMAZE-08) with the surface SFG spectra of the compounds surveyed here, yet we cannot rule out this mismatch being attributable to differences in molecular orientation. The implications of our findings for SOA formation are discussed in the context of condensational particle growth and reactivity.

Plasmon-enhanced spectral changes in surface sum-frequency generation with polychromatic light

We theoretically explore the spectral behavior of the fundamental and sum-frequency waves generated from the surface of a thin metal film in the Kretschmann configuration with coherent ultrashort pulses. We show that the spectra of reflected sum-frequency waves exhibit pronounced shifts for the incident fundamental waves close to the plasmon coupling angle. We also demonstrate that the scale of discovered plasmon-enhanced spectral changes is strongly influenced by the magnitude of the incidence angle and the bandwidth of the source spectrum.

Correction to “Basic Theory of Surface Sum-Frequency Generation”

Correction to “Basic Theory of Surface Sum-Frequency Generation”

Solvent quality affects chain conformational order at the polymer surface revealed by sum frequency generation vibrational spectroscopy

The surface sum frequency generation (SFG) vibrational spectroscopic spectra of PMA and PMMA films prepared from solvents with different qualities were found different. This suggests that the surface molecular structures of PMA and PMMA films were affected by the solvent quality. A simple phenomenological model was used to describe the chain conformational order at the polymer surface by correlating the SFG resonant signals of the side chromophoric groups to the introduced chain arc included angle. This model is believed to be applicable for polymers with short and rigid side chromophores active for the SFG spectroscopy.

Unified treatment and measurement of the spectral resolution and temporal effects in frequency-resolved sum-frequency generation vibrational spectroscopy (SFG-VS)

The lack of understanding of the temporal effects and the restricted ability to control experimental conditions in order to obtain intrinsic spectral lineshapes in surface sum-frequency generation vibrational spectroscopy (SFG-VS) have limited its applications in surface and interfacial studies. The emergence of high-resolution broadband sum-frequency generation vibrational spectroscopy (HR-BB-SFG-VS) with sub-wavenumber resolution [Velarde et al., J. Chem. Phys., 2011, 135, 241102] offers new opportunities for obtaining and understanding the spectral lineshapes and temporal effects in SFG-VS. Particularly, the high accuracy of the HR-BB-SFG-VS experimental lineshape provides detailed information on the complex coherent vibrational dynamics through direct spectral measurements. Here we present a unified formalism for the theoretical and experimental routes for obtaining an accurate lineshape of the SFG response. Then, we present a detailed analysis of a cholesterol monolayer at the air/water interface with higher and lower resolution SFG spectra along with their temporal response. With higher spectral resolution and accurate vibrational spectral lineshapes, it is shown that the parameters of the experimental SFG spectra can be used both to understand and to quantitatively reproduce the temporal effects in lower resolution SFG measurements. This perspective provides not only a unified picture but also a novel experimental approach to measuring and understanding the frequency-domain and time-domain SFG response of a complex molecular interface.

Erratum: “Observation of buried water molecules in phospholipid membranes by surface sum-frequency generation spectroscopy” [J. Chem. Phys. 131, 161107 (2009)

First Page

Furan Hydrogenation over Pt(111) and Pt(100) Single-Crystal Surfaces and Pt Nanoparticles from 1 to 7 nm: A Kinetic and Sum Frequency Generation Vibrational Spectroscopy Study

Sum frequency generation surface vibrational spectroscopy and kinetic measurements using gas chromatography have been used to systematically study the adsorption and hydrogenation of furan over Pt(111) and Pt(100) single-crystal surfaces and size-controlled 1.0-nm, 3.5-nm and 7.0-nm Pt nanoparticles at Torr pressures (10 Torr of furan, 100 Torr of H(2)) to form dihydrofuran, tetrahydrofuran, and the ring-cracking products butanol and propylene. As determined by SFG, the furan ring lies parallel to all Pt surfaces studied under hydrogenation conditions. Upright THF and the oxametallacycle intermediate are observed over the nanoparticle catalysts under reaction conditions. Butoxy increases in surface concentration over Pt(111) with increasing temperature in agreement with selectivity trends.