Heterodyne-detected Vibrational Sum Frequency Generation Research Articles

Quadrupolar mechanism for vibrational sum frequency generation at air/liquid interfaces: Theory and experiment

Vibrational sum frequency generation (VSFG) spectroscopy has been widely utilized to investigate various interfaces through molecular vibration. VSFG is usually attributed to the breakdown of the inversion symmetry at the interface within the electric dipole approximation. Although the electric dipole approximation is a very good approximation in the isotropic bulk, its validity is questionable at the interface because a large electric field gradient exists in the thin interface region. Thus, the quadrupole contribution may become significant at the interface. Here, we discuss the quadrupole contribution in VSFG from theoretical and experimental viewpoints. We describe a theory as to how the quadrupole contribution appears in experimental VSFG spectra by deriving the vibrational selection rule and discussing the interface selectivity. With this theoretical framework, we examine the mechanism of VSFG at the air/benzene and air/decane interfaces. The accurate determination of the vibrational frequencies realized by heterodyne-detected VSFG spectroscopy reveals that VSFG at the air/benzene interface arises from the quadrupolar mechanism. This means that the observation of VSFG does not imply a molecular alignment so that interfacial benzene molecules may be randomly oriented. Meanwhile, at the air/decane interface, it is concluded that the VSFG signal arises from the ordinary dipolar mechanism. This implies that decane molecules are aligned in a preferential direction at the interface despite their low polarity. This study demonstrates the importance of examining the mechanism of VSFG before discussing the interfacial structure based on VSFG spectra. A strategy to distinguish different mechanisms is also proposed. The present study further shows that the quadrupolar mechanism, if properly taken into consideration, enables us to obtain information about interfacial molecules beyond the restriction of the inversion symmetry breaking required by the dipolar mechanism, through the large electric field gradient localized at the interface.

Molecular structure of a hyperactive antifreeze protein adsorbed to ice.

Antifreeze proteins (AFPs) are a unique class of proteins that bind to ice crystal surfaces and arrest their growth. The working mechanism of AFPs is not well understood because, as of yet, it was not possible to perform molecular-scale studies of AFPs adsorbed to the surface of ice. Here, we study the structural properties of an AFP from the insect Rhagium mordax (RmAFP) adsorbed to ice with surface specific heterodyne-detected vibrational sum-frequency generation spectroscopy and molecular dynamic simulations. We find that RmAFP, unlike other proteins, retains its hydrating water molecules upon adsorption to the ice surface. This hydration water has an orientation and hydrogen-bond structure different from the ice surface, thereby inhibiting the insertion of water layers in between the protein and the ice surface.

Polyatomic Iodine Species at the Air-Water Interface and Its Relevance to Atmospheric Iodine Chemistry: An HD-VSFG and Raman-MCR Study.

Iodine plays a key role in tropospheric ozone destruction, atmospheric new particle formation, as well as growth. Air-water interface happens to be an important reaction site pertaining to such phenomena. However, except iodide (I-), the behavior of other iodine species, for example, triiodide (I3-) and iodate (IO3-, the most abundant iodine species in seawater) at the aqueous interface and their effect on the interfacial water are largely unknown. Using interface-specific vibrational spectroscopy (heterodyne-detected vibrational sum frequency generation), we recorded the imaginary-χ(2) spectra (Imχ(2); χ(2) is the second-order electric susceptibility in OH stretch region) of the air-water interface in the presence of IO3-, I3-, and I- (≤0.3 M) in the aqueous subphase. The Imχ(2) spectra reveal that the chaotropic I3- is the most surface-active anion among the iodine species studied and decreases the vibrational coupling and hydrogen-bonding of interfacial water. Interestingly, the IO3-, even being a kosmotrope, is quite prevalent in the interfacial region and preferentially orients the interfacial water as "H-down" (i.e., water dipole moment is pointed toward the bulk water). Mapping of the OH stretch response of ion-affected water at interface (i.e., ΔImχ(2) = Imχ(2)air-water-iodinesalt - Imχ(2)air-water) with that in the hydration shell of the respective ion (hydration shell water response is obtained by Raman multivariate curve resolution spectroscopy) reveals a correlative link between the ion's influence on the interfacial water and their hydration shell structure. The distinct water structure of stronger as well as weaker H-bonding in the hydration shell of the polyatomic IO3- anion promotes the anion to stay at the interfacial region. Thus, the surface prevalence of the iodine species and their effect on the interfacial water are perceived to be crucial for the transfer of iodine from seawater to the atmosphere across the marine boundary layer and the chemistry of iodine at aqueous aerosol surface.

Effect of hydrogen-bond on ultrafast spectral diffusion dynamics of water at charged monolayer interfaces.

Ultrafast hydrogen-bond fluctuation dynamics of water at charged monolayer interfaces were studied by the use of steady-state and 2D heterodyne-detected vibrational sum frequency generation (HD-VSFG) spectroscopy. Specifically, the effect of hydrogen-bond ability of the interface on the dynamics was investigated by comparing two monolayer interfaces that provide different hydrogen bond abilities: hydrogen bonding octadecylammonium (ODA) monolayer (pH = 2) and non-hydrogen bonding 1,2-dipalmitoyl-3-trimethyl-ammonium propane (DPTAP) monolayer. The steady-state HD-VSFG spectra and their ionic strength dependence revealed that water molecules at both of ODA and DPTAP interfaces are H-down oriented, pointing their H away from the interface, and that the contributions of the electrical double layer in the interfacial spectra of these interfaces are comparable to each other. However, 2D HD-VSFG data clearly indicated that the ultrafast hydrogen-bond fluctuation of water at the ODA interface is significantly suppressed, compared to that at the DPTAP interfaces. The obtained results suggest that the hydrogen-bond fluctuation of the topmost interfacial water at a positively charged interface is significantly affected by the hydrogen-bonding ability of the interface even in the case that the interfacial water molecules act as a hydrogen-bond acceptor to the head group of the monolayer.

Publisher's Note: "Bulk-or-interface assignment of heterodyne-detected chiral vibrational sum frequency generation signal by its polarization dependence" [J. Chem. Phys. 149, 244703 (2018)

Publisher's Note: "Bulk-or-interface assignment of heterodyne-detected chiral vibrational sum frequency generation signal by its polarization dependence" [J. Chem. Phys. 149, 244703 (2018)

Bulk-or-interface assignment of heterodyne-detected chiral vibrational sum frequency generation signal by its polarization dependence.

Polarization dependence of heterodyne-detected chiral vibrational sum frequency generation (VSFG) was examined for thin films of polylactic acids and neat limonene liquid far from electronic resonance. The enantiomers of polylactic acid films on silica substrates were successfully distinguished, and their chiral VSFG signals were ascribed not to bulk but to the interfaces by comparing chiral signals observed in reflection in the S-polarized VSFG, P-polarized visible, and P-polarized infrared and P-polarized VSFG, S-polarized visible, and P-polarized infrared polarization combinations with theoretical model calculations. In the same way, the chiral VSFG signal of neat limonene was assigned to bulk, which is consistent with the previous assignment. The method employed for assigning the source of chiral signals to the bulk or the interface may be useful for organic films on substrates with low refractive indices and thick samples.

Heterodyne-Detected Vibrational Sum Frequency Generation Study of Air–Water–Fluoroalcohol Interface: Fluorocarbon Group-Induced Structural and Orientational Change of Interfacial Water

The presence of fluorocarbon group in alcohols provides them unique and important physicochemical properties. Fluoroalcohol containing aqueous interfaces are used in diverse fields, such as liquid–liquid phase separation, chemical reactions, and polymer industry, and so forth. However, the molecular level understanding of interfacial water in the presence of fluorinated alcohol is sparse. In this paper, we have applied phase-sensitive and surface-specific vibrational spectroscopic technique, heterodyne-detected vibrational sum frequency generation, to understand the structure and orientation of interfacial water in the presence of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP). To realize the role of fluorination, the results of the air–water–HFIP interface have been compared with the corresponding hydrogenated alcohol, air–water–isopropanol (IP) interface. It is observed that the net orientation (H-down) and hydrogen bonding of water at the air–water–IP interface are similar to the neat air–water interface. In contrast, water changes its net orientation (H-up) and becomes more inhomogeneous at the air–water–HFIP interface. On increasing the bulk pH (11), the interfacial water becomes increasingly ordered (H-up oriented) at the air–water–HFIP interface, whereas there is no significant change at the air–water–IP interface. At acidic pH (2.8), the interfacial water takes the same H-down orientation for both IP and HFIP, though the average H-bonding is stronger for HFIP. Thus, fluorination of IP changes the preferred orientation and structure of interfacial water, which may be useful in understanding chemical and biochemical processes that occur at fluoroalcohol-containing aqueous interfaces.

Surface Structure of Solutions of Poly(vinyl alcohol) in Water.

We use surface-specific heterodyne-detected vibrational sum-frequency generation spectroscopy (HD-VSFG) and surface tension measurements to investigate the molecular structure of the surface of aqueous solutions of poly(vinyl alcohol) (PVA) polymers with average molecular weights of 10000 and 125000 g/mol. We find that the interfacial water molecules have a preferred orientation with their hydrogen-bonded O-H groups pointing away from the bulk, for both PVA10000 and PVA125000. This observation is explained from the ongoing hydrolysis of the acetyl impurities on the PVA polymer chains. This hydrolysis yields negatively charged acetate ions that have a relatively high surface propensity. For both PVA10000 and PVA125000 the strong positive signal vanishes when the pH is decreased, due to the neutralization of the acetate ions. For solutions with a high concentration of PVA10000 the interfacial water signal becomes very small, indicating that the surface gets completely covered with a disordered PVA polymer film. In contrast, for high concentrations of PVA125000, the strong positive water signal persists at high pH, which shows that the water surface does not get completely covered. The HD-VSFG data combined with surface tension data indicate that concentrated PVA125000 solutions form a structured surface layer with pores containing a high density of interfacial water.

Molecular mechanism of charge inversion revealed by polar orientation of interfacial water molecules: A heterodyne-detected vibrational sum frequency generation study.

"Charge inversion" is a phenomenon in which multivalent counterions overcompensate for interfacial charges and invert the sign of the net charge near a surface. This phenomenon is believed to be relevant to biologically important processes such as DNA condensation, and hence it has attracted much attention. We investigated the polar orientation of interfacial water molecules at two different negatively charged interfaces in the absence and presence of La3+ using heterodyne-detected vibrational sum frequency generation spectroscopy, which can directly determine the up/down orientation of interfacial molecules. It was found that the orientations of water molecules at a bio-relevant phospholipid interface change from the hydrogen-up to the hydrogen-down with the addition of 10 µM La3+. This change of water orientation indicates that the net charge at the phospholipid interface is inverted by adsorption of La3+ to the phosphate headgroup. By contrast, at an alkylsulfate interface, the majority of the interfacial water molecules remain hydrogen-up orientated even in the presence of 25 mM La3+, indicating that the sulfate headgroup is still solvated by up-oriented water. The observed headgroup specificity suggests that charge inversion at the phospholipid interface originates primarily from the chemical interaction between the phosphate and La3+ ion.

The Topmost Water Structure at a Charged Silica/Aqueous Interface Revealed by Heterodyne-Detected Vibrational Sum Frequency Generation Spectroscopy.

Despite recent significant advances in interface-selective nonlinear spectroscopy, the topmost water structure at a charged silica surface is still not clearly understood. This is because, for charged interfaces, not only interfacial molecules at the topmost layer but also a large number of molecules in the electric double layer are probed even with second-order nonlinear spectroscopy. In the present study, we studied water structure at the negatively charged silica/aqueous interface at pH 12 using heterodyne-detected vibrational sum frequency generation spectroscopy, and demonstrated that the spectral component of the topmost water can be extracted by examining the ionic strength dependence of the Imχ(2) spectrum. The obtained Imχ(2) spectrum indicates that the dominant water species in the topmost layer is hydrogen-bonded to the negatively charged silanolate at the silica surface with one OH group. There also exists minor water species that weakly interacts with the oxygen atom of a siloxane bridge or the remaining silanol at the silica surface, using one OH group. The ionic strength dependence of the Imχ(2) spectrum indicates that this water structure of the topmost layer is unchanged in a wide ionic strength range from 0.01 to 2 M.

Electrical Double Layer Probed by Surface-Specific Vibrational Technique

In this issue of Chem, Paesani and co-workers present a computational analysis of sum-frequency generation (SFG) spectra of water to disentangle the interfacial χ(2) and bulk χ(3) contributions. SFG line shapes are in good agreement with experimental results. The analysis reveals the molecular response of interfacial water, which is usually masked by the bulk water spectra at the water-charged surfactant interface.

Molecular dynamics study of structure and vibrational spectra at zwitterionoic lipid/aqueous KCl, NaCl, and CaCl2 solution interfaces.

Molecular dynamics (MD) simulations of KCl, NaCl, and CaCl2 solution/dipalmytoylphosphatidylcholine lipid interfaces were performed to analyze heterodyne-detected vibrational sum frequency generation (HD-VSFG) spectra in relation to the interfacial water structure. The present MD simulation well reproduces the experimental spectra and elucidates a specific cation effect on the interfacial structure. The K+, Na+, and Ca2+ cation species penetrate in the lipid layer more than the anions in this order, due to the electrostatic interaction with negative polar groups of lipid, and the electric double layer between the cations and anions cancels the intrinsic orientation of water at the water/lipid interface. These mechanisms explain the HD-VSFG spectrum of the water/lipid interface and its spectral perturbation by adding the ions. The lipid monolayer reverses the order of surface preference of the cations at the solution/lipid interface from that at the solution/air interface.

Structure at the air/water interface in the presence of phenol: a study using heterodyne-detected vibrational sum frequency generation and molecular dynamics simulation

Many kinds of organic compounds pollute the aquatic environment, and they change the properties of the water surface due to their high surface affinity. Chemical reactions at the water surface are key in environmental chemistry because, for instance, reactions occurring at the surface of aqueous aerosols play essential roles in the atmosphere. Therefore, it is very important to elucidate how organic compounds affect the properties of water surfaces. Here, we choose phenol as an organic pollutant prototype and report how phenol affects the molecular-level structure of the air/water interface. Interface-selective vibrational spectra, i.e., the imaginary part of second-order nonlinear susceptibility (Im χ(2)), of the air/water-phenol mixture interface in the OH stretch region were collected using heterodyne-detected vibrational sum frequency generation (HD-VSFG) spectroscopy, and the observed Im χ(2) spectra were interpreted with the aid of molecular dynamics (MD) simulation. The Im χ(2) spectra observed via HD-VSFG drastically change as a function of phenol concentration in water, and exhibit two isosbestic points. In the spectra, a positive OH band appears at 3620 cm-1, which is assigned to an OH group of water that forms an OHπ hydrogen-bond (H-bond) with the aromatic ring of phenol, and a strong negative OH band appears around 3200 cm-1, which is attributed to a water that accepts a H-bond from the phenol OH, while pointing its OH groups toward the bulk water side. It was concluded that two types of unique water molecules hydrate a phenol molecule: (1) water that forms an OHπ H-bond; and (2) water that accepts a H-bond from a phenol OH group. Each phenol molecule adsorbed at the air/water forms a specific hydration structure, which causes a large change in the interfacial water structure. The present study provides a clear example demonstrating that even such a simple organic pollutant as phenol can drastically alter the interfacial water structure.

The structure of a lanthanide complex at an extractant/water interface studied using heterodyne-detected vibrational sum frequency generation.

Solvent extraction plays an integral part in the separation and purification of metals. Because extractants generally used as complexing agents for metal extractions, such as di-(2-ethylhexyl)phosphoric acid (HDEHP) for lanthanide extractions, are amphiphilic, they come to an organic/water interface, and the interface plays a crucial role as the site of the formation of metal complexes and the subsequent transfer reaction to an organic phase. Despite the importance of the interface for metal solvent extractions, its molecular-level structure is unclear because of the experimental difficulties. Here we studied the structure of a trivalent europium (Eu3+) complex with HDEHP formed at the HDEHP monolayer/water interface using heterodyne-detected vibrational sum frequency generation (HD-VSFG) spectroscopy. The study on the HDEHP/water interface enables us to investigate the structure of the interfacial Eu3+ complex by excluding the migration of Eu3+ into an organic phase after the complex formation at the interface. The interface-selective vibrational Imχ(2) spectra observed using HD-VSFG of the interface of HDEHP/aqueous Eu(NO3)3 solution in the 2800-3500 cm-1 region indicate that Eu3+ at the HDEHP/water interface is bonded by HDEHP from the air side and by water molecules from the water side. To the best of our knowledge, such metal complex structures have not been identified in organic or water solutions.

Development of Heterodyne-Detected Total Internal Reflection Vibrational Sum Frequency Generation Spectroscopy and Its Application to CaF2/Liquid Interfaces

We present heterodyne-detected total internal reflection vibrational sum frequency generation (HD-TIR VSFG) spectroscopy for CaF2/liquid interfaces. With this technique, absolute orientations at solid/liquid interfaces can be determined by measuring complex χ(2) spectra of the buried interfaces. We applied the technique to CaF2/sodium dodecyl sulfate (SDS) solution interfaces, and directly determined the polar orientations of the water molecules and surfactants at the interface based on the phase information on VSFG spectra, which is unavailable in conventional homodyne-detected TIR VSFG spectroscopy. The reorientation of the interfacial water molecules was observed as a change of the sign of Im[χ(2)] depending on the surfactant concentration.

Orientation of Methylguanidinium Ions at the Water-Air Interface.

We use heterodyne-detected vibrational sum-frequency generation (HD-VSFG) to determine the orientation of the molecular plane of methylguanidinium ions at the surface of aqueous solutions. We measure the VSFG response of the symmetric and antisymmetric methyl stretch vibrations of the methylguanidinium ion with different polarization combinations. We find that for at least 50% of the methylguanidinium ions the molecular plane is at an angle >20° with respect to the surface plane. Hence, for only a minor fraction of the ions does the molecular plane have an orientation (near-)parallel to the surface plane, in contrast to the predictions of recent molecular dynamics simulation studies.

Cooperative Hydrogen-Bond Dynamics at a Zwitterionic Lipid/Water Interface Revealed by 2D HD-VSFG Spectroscopy

Molecular-level elucidation of hydration at biological membrane interfaces is of great importance for understanding biological processes. We studied ultrafast hydrogen-bond dynamics at a zwitterionic phosphatidylcholine/water interface by two-dimensional heterodyne-detected vibrational sum frequency generation (2D HD-VSFG) spectroscopy. The obtained 2D spectra confirm that the anionic phosphate and cationic choline sites are individually hydrated at the interface. Furthermore, the data show that the dynamics of water at the zwitterionic lipid interface is not a simple sum of the dynamics of the water species that hydrate to the separate phosphate and choline. The center line slope (CLS) analysis of the 2D spectra reveals that ultrafast hydrogen-bond fluctuation is not significantly suppressed around the phosphate at the zwitterionic lipid interface, which makes the hydrogen-bond dynamics look similar to that of the bulk water. The present study indicates that the hydrogen-bond dynamics at membrane interfaces is not determined only by the hydrogen bond to a specific site of the interface but is largely dependent on the water dynamics in the vicinity and other nearby moieties, through the hydrogen-bond network.

Ultrafast Dynamics at Water Interfaces Studied by Vibrational Sum Frequency Generation Spectroscopy.

We present an overview of studies on the ultrafast dynamics of water at aqueous interfaces carried out by time-resolved vibrational sum frequency generation (VSFG) spectroscopies. This research field has been growing rapidly, stimulated by technical developments achieved recently. In this review, first, the principles and instrumentations are described for conventional VSFG, heterodyne-detected VSFG, and various IR-pump/VSFG-probe techniques, namely, time-resolved conventional VSFG, time-resolved heterodyne-detected VSFG, and their extension to two-dimensional spectroscopy. Second, the applications of these time-resolved VSFG techniques to the study of the femtosecond vibrational dynamics of water at various interfaces are discussed, in the order of silica/water, charged monolayer/water, and the air/water interfaces. These studies demonstrate that there exists water dynamics specific to the interfaces and that time-resolved VSFG spectroscopies can unambiguously detect such unique dynamics in an interface-selective manner. In particular, the most recent time-resolved heterodyne-detected VSFG and two-dimensional heterodyne-detected VSFG unveil the inhomogeneity of the hydrogen bond and relevant vibrational dynamics of interfacial water through unambiguous observation of hole-burning in the OH stretch band, as well as the subsequent spectral diffusion in the femtosecond time region. These time-resolved VSFG studies have also left several issues for discussion. We describe not only the obtained conclusive physical insights into interfacial water dynamics but also the points left unclear or controversial. A new type of experiment that utilizes UV excitation is also described briefly. Lastly, the summary and some future perspectives of time-resolved VSFG spectroscopies are given.

Heterodyne-Detected Sum Frequency Generation Study of Adsorption of I– at Model Paint–Water Interface and Its Relevance to Post-Nuclear Accident Scenario

Organic iodides constitute a significant fraction of radioactive iodine released into the environment in the event of a nuclear power plant accident. The painted surfaces inside the reactor containment play a key role in the formation of organic iodides. In this study, heterodyne detected vibrational sum frequency generation (HD-VSFG) spectroscopy has been used to gain insight into the origin of organic iodides from paint surfaces. Model polymeric compounds dimethylhexadecyl amine (DHDA) and Nylon6, which resemble the constituents of containment paints, are selected for this study. Our investigations on the DHDA–water interface and Nylon6–water interface reveal the existence of positive surface field at acidic conditions (bulk pH: 2, 6) due to protonation at amine functional group and adsorption of H+ at amide groups; and a negative surface field at pH 11 due to adsorption of OH– ions at both amine and amide functional groups. In the presence of CsI in the aqueous phase, this surface field is altered by t...

Alkyl Chain Length Dependent Structural and Orientational Transformations of Water at Alcohol-Water Interfaces and Its Relevance to Atmospheric Aerosols.

Although the hydrophobic size of an amphiphile plays a key role in various chemical, biological, and atmospheric processes, its effect at macroscopic aqueous interfaces (e.g., air-water, oil-water, cell membrane-water, etc.), which are ubiquitous in nature, is not well understood. Here we report the hydrophobic alkyl chain length dependent structural and orientational transformations of water at alcohol (CnH2n+1OH, n = 1-12)-water interfaces using interface-selective heterodyne-detected vibrational sum frequency generation (HD-VSFG) and Raman multivariate curve resolution (Raman-MCR) spectroscopic techniques. The HD-VSFG results reveal that short-chain alcohols (CnH2n+1OH, n < 4, i.e., up to 1-propanol) do not affect the structure (H-bonding) and orientation of water at the air-water interface; the OH stretch band maximum appears at ∼3470 cm-1, and the water H atoms are pointed toward the bulk water, that is, "H-down" oriented. In contrast, long-chain alcohols (CnH2n+1OH, n > 4, i.e., beyond 1-butanol) make the interfacial water more strongly H-bonded and reversely orientated; the OH stretch band maximum appears at ∼3200 cm-1, and the H atoms are pointed away from the bulk water, that is, "H-up" oriented. Interestingly, for the alcohol of intermediate chain length (CnH2n+1OH, n = 4, i.e, 1-butanol), the interface is quite unstable even after hours of its formation and the time-averaged result is qualitatively similar to that of the long-chain alcohols, indicating a structural/orientational crossover of interfacial water at the 1-butanol-water interface. pH-dependent HD-VSFG measurements (with H2O as well as isotopically diluted water, HOD) suggest that the structural/orientational transformation of water at the long-chain alcohol-water interface is associated with the adsorption of OH- anion at the interface. Vibrational mapping of the water structure in the hydration shell of OH- anion (obtained by Raman-MCR spectroscopy of NaOH in HOD) clearly shows that the water becomes strongly H-bonded (OH stretch max. ≈ 3200 cm-1) while hydrating the OH- anion. Altogether, it is conceivable that alcohols of different hydrophobic chain lengths that are present in the troposphere will differently affect the interfacial electrostatics and associated chemical processes of aerosol droplets, which are critical for cloud formation, global radiation budget, and climate change.