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Terahertz molecular motions are often probed by high-frequency molecular oscillators in different types of non-linear vibrational spectroscopy. Recently developed two-dimensional terahertz-infrared-visible spectroscopy allows direct measuring of this coupling and, thus, obtaining site-specific terahertz vibrational spectrum. However, these data are affected by the intensity and phase of the employed laser pulses. In this work, we develop a method of extracting sample response—representing solely physical properties of a material—from experimental spectra. Using dimethyl sulfoxide as a model molecule to verify this method, we measure the coupling between C–H stretch vibration of its methyl groups and terahertz intramolecular twist and wagging modes. [ABSTRACT FROM AUTHOR]

We report the vibrational and orientational dynamics of water molecules in isotopically diluted NaOH and NaOD solutions using polarization-resolved femtosecond vibrational spectroscopy and terahertz time-domain dielectric relaxation measurements. We observe a speed-up of the vibrational relaxation of the O-D stretching vibration of HDO molecules outside the first hydration shell of OH- from 1.7 ± 0.2 ps for neat water to 1.0 ± 0.2 ps for a solution of 5 M NaOH in HDO:H2O. For the O-H vibration of HDO molecules outside the first hydration shell of OD-, we observe a similar speed-up from 750 ± 50 fs to 600 ± 50 fs for a solution of 6 M NaOD in HDO:D2O. The acceleration of the decay is assigned to fluctuations in the energy levels of the HDO molecules due to charge transfer events and charge fluctuations. The reorientation dynamics of water molecules outside the first hydration shell are observed to show the same time constant of 2.5 ± 0.2 ps as in bulk liquid water, indicating that there is no long range effect of the hydroxide ion on the hydrogen-bond structure of liquid water. The terahertz dielectric relaxation experiments show that the transfer of the hydroxide ion through liquid water involves the simultaneous motion of ∼7 surrounding water molecules, considerably less than previously reported for the proton. [ABSTRACT FROM AUTHOR]

We investigate the structure and orientation of water molecules at the water-lipid interface, using vibrational sum-frequency generation in conjunction with a maximum entropy phase retrieval method. We find that interfacial water molecules have an orientation opposite to that predicted by electrostatics and thus are likely localized between the lipid headgroup and its apolar alkyl chain. This type of water molecule is observed for phospholipids but not for structurally simpler surfactants. [ABSTRACT FROM AUTHOR]

We present an experimental and theoretical study of vibrational excitation of the C–O stretch vibration of carbon monoxide adsorbed on a ruthenium Ru(001) surface with ultrashort femtosecond infrared laser pulses. After broadband excitation leading to transfer of a significant fraction of the CO molecules to their first (∼15%) and second (∼5%) vibrationally excited states, we observe a competition between vibrational energy relaxation and energy delocalization through dipole–dipole coupling. We reproduce the observed excited state spectra by solving the three-level Bloch equations and accounting for intermolecular vibrational energy transfer on a picosecond time scale. The rate of vibrational energy transfer, and its coverage-dependence, can be described by a Fo¨rster energy transfer mechanism. We discuss possibilities to optimize the degree of localized vibrational excitation of a specific bond of molecules at surfaces through chirped pulse IR excitation. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Small organic molecules on ice and water surfaces are ubiquitous in nature and play a crucial role in many environmentally relevant processes. Herein, we combine surface‐specific vibrational spectroscopy and a controllable flow cell apparatus to investigate the molecular adsorption of acetone onto the basal plane of single‐crystalline hexagonal ice with a large surface area. By comparing the adsorption of acetone on the ice/air and the water/air interface, we observed two different types of acetone adsorption, as apparent from the different responses of both the free O−H and the hydrogen‐bonded network vibrations for ice and liquid water. Adsorption on ice occurs preferentially through interactions with the free OH group, while the interaction of acetone with the surface of liquid water appears less specific. Small organic molecules on ice and water surfaces play crucial roles in many environmentally relevant processes. Surface‐specific vibrational spectroscopy was combined with a controllable flow cell apparatus to investigate the molecular adsorption of acetone onto the basal plane of single‐crystalline hexagonal ice with a large surface area. [ABSTRACT FROM AUTHOR]

Knowledge of the interfacial water structure is essential for a basic understanding of the many environmental, technological, and biophysical systems in which aqueous interfaces appear. Using ultrafast two-dimensional surface-specific vibrational spectroscopy we show that the structure of heavy water at the water-air interface displays short-lived heterogeneity and is very different from that at the water-lipid interface. [ABSTRACT FROM AUTHOR]

Water interfaces provide the platform for many important biological, chemical, and physical processes. The water-air interface is the most common and simple aqueous interface and serves as a model system for water at a hydrophobic surface. Unveiling the microscopic (<1 nm) structure and dynamics of interfacial water at the water-vapor interface is essential for understanding the processes occurring on the water surface. At the water interface the network of very strong intermolecular interactions, hydrogen-bonds, is interrupted and the density of water is reduced. A central question regarding water at interfaces is the extent to which the structure and dynamics of water molecules are influenced by the interruption of the hydrogen-bonded network and thus differ from those of bulk water. Herein, we discuss recent advances in the study of interfacial water at the water-air interface using laser-based surface-specific vibrational spectroscopy. [ABSTRACT FROM AUTHOR]

The surface vibrational spectrum of water at biological interfaces is often interpreted as having 'ice-like' and 'liquid-like' components. Here we show that the vibrational spectrum of water at both water-lipid and water-protein interfaces greatly simplifies upon H/D isotopic dilution, which is inconsistent with the presence of 'ice-like' structures. The changes in the spectra as a function of isotope content can be explained by intramolecular coupling between bend and stretch vibrations of the water molecules. [ABSTRACT FROM AUTHOR]

We present a novel setup to elucidate the dynamics of interfacial molecules specifically, using surface-selective femtosecond vibrational spectroscopy. The approach relies on a fourth-order nonlinear optical interaction at the interface. In the experiments, interfacial molecules are vibrationally excited by an intense, tunable femtosecond midinfrared (2500–3800 cm-1) pump pulse, resonant with the molecular vibrations. The effect of the excitation and the subsequent relaxation to the equilibrium state are probed using broadband infrared+visible sum frequency generation (SFG) light, which provides the transient vibrational spectrum of interfacial molecules specifically. This IR pump-SFG probe setup has the ability to measure both vibrational population lifetimes as well as the vibrational coupling between different chemical moieties at interfaces. Vibrational lifetimes of interfacial molecules are determined in one-dimensional pump-SFG probe experiments, in which the response is monitored as a function of the delay between the pump and probe pulses. Vibrational coupling between molecular groups is determined in two-dimensional pump-SFG probe experiments, which monitor the response as a function of pump and probe frequencies at a fixed delay time. To allow for one setup to perform these multifaceted experiments, we have implemented several instrumentation techniques described here. The detection of the spectrally resolved differential SFG signal using a combination of a charge-coupled device camera and a piezocontrolled optical scanner, computer-controlled Fabry–Pérot etalons to shape and scan the IR pump pulse and the automated sample dispenser and sample trough height corrector are some of the novelties in this setup. [ABSTRACT FROM AUTHOR]

Abstract: The phase behavior of bilayers of binary mixtures of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and cholesterol has been studied using Raman spectroscopy. It is observed that the shape of the cholesterol vibrational spectrum in lipid–cholesterol binary mixtures does not vary significantly with either the cholesterol concentration or the temperature. This permits determination of the lipid vibrational signatures of the liquid-disordered (ld), solid-ordered (so) and liquid-ordered (lo) phases. Within the phase coexistence region, the measured spectra are described very well by a linear combination of the different spectral components, which permits a quantitative analysis of the phase diagram. In contrast to earlier findings, our experiments provide no indication of a phase boundary at low cholesterol concentration. The upper boundary of the phase coexistence region is found at ∼27 and ∼22mol% for ld–lo and so–lo coexistence region, respectively. Within these phase coexistence regions, the partitioning of cholesterol between the cholesterol-poor and the cholesterol-rich phases is in close agreement with the lever rule. [Copyright &y& Elsevier]

Cell-penetrating peptides (CPPs) are short membrane-permeating amino acid sequences that can be used to deliver cargoes, e.g. drugs, into cells. The mechanism for CPP internalization is still subject of ongoing research. An interesting family of CPPs is the sweet arrow peptides – SAP(E) – which are known to adopt a polyproline II helical secondary structure. SAP(E) peptides stand out among CPPs because they carry a net negative charge while most CPPs are positively charged, the latter being conducive to electrostatic interaction with generally negatively charged membranes. For SAP(E)s, an internalization mechanism has been proposed, based on polypeptide aggregation on the cell surface, followed by an endocytic uptake. However, this process has not yet been observed directly – since peptide–membrane interactions are inherently difficult to monitor on a molecular scale. Here, we use sum frequency generation (SFG) vibrational spectroscopy to investigate molecular interactions of SAP(E) with differently charged model membranes, in both mono- and bi-layer configurations. The data suggest that the initial binding mechanism is accompanied by structural changes of the peptide. Also, the peptide-model membrane interaction depends on the charge of the lipid headgroup with phosphocholine being a favorable binding site. Moreover, while direct penetration has also been observed for some CPPs, the spectroscopy reveals that for SAP(E), its interaction with model membranes remains limited to the headgroup region, and insertion into the hydrophobic core of the lipid layer does not occur. [ABSTRACT FROM AUTHOR]

We present an overview of recent static and time-resolved vibrational spectroscopic studies of liquid water from ambient conditions to the supercooled state, as well as of crystalline and amorphous ice forms. The structure and dynamics of the complex hydrogen-bond network formed by water molecules in the bulk and interphases are discussed, as well as the dissipation mechanism of vibrational energy throughout this network. A broad range of water investigations are addressed, from conventional infrared and Raman spectroscopy to femtosecond pump--probe, photon-echo, optical Kerr effect, sum-frequency generation, and two-dimensional infrared spectroscopic studies. Additionally, we discuss novel approaches, such as two-dimensional sum-frequency generation, three-dimensional infrared, and two-dimensional Raman terahertz spectroscopy. By comparison of the complementary aspects probed by various linear and nonlinear spectroscopic techniques, a coherent picture of water dynamics and energetics emerges. Furthermore, we outline future perspectives of vibrational spectroscopy for water researches. [ABSTRACT FROM AUTHOR]

We report a combined vibrational sum-frequency generation(SFG)spectroscopy, Brewster angle microscopy (BAM), and ellipsometry studyof different surfactants on water as a function of surfactant density.Vibrational SFG spectra of surfactants on the water surface in a Langmuirtrough have been measured in both the surfactant CH and the waterOH stretch regions. At low densities, the SFG signal generated atthe surface in the presence of the surfactant is indistinguishablefrom the SFG signal generated at the clean water–air interface.When the surfactant density increases, i.e., upon compressing themonolayer, a very sudden increase in the SFG signal in both the CHand OH spectral regions is observed. For higher laser fluences, thisstepwise increase occurs at increasingly higher surfactant densities.Since BAM shows that surfactant molecules are clearly present at theselow densities, we conclude that at low surfactant density the laserbeam displaces relatively high-density domains with surfactants inthe liquid expanded phase out of the region of the laser focus. Thisis a consequence of the thermal gradient induced by local heatingof the water phase with the monolayer on top due to repetitive laserexcitation at 1 kHz. It can be circumvented by using a rotating trough.In this manner, the sampled surface area can be refreshed, allowingartifact-free vibrational SFG spectra to be measured down to the verylowest surfactant densities. In ellipsometry experiments, a similarstep can be noticed, which, however, is of a different nature; i.e.,it is not related to heating (the laser fluence is very low and thelight nonresonant) but to a molecular transition. The occurrence ofthe step in ellipsometry as a function of area per molecule dependscritically on the preparation of the monolayer. By giving the moleculestime and space to relax during the preparation of the monolayer, thisstep could also be eliminated. [ABSTRACT FROM AUTHOR]

As a surface-specific technique, vibrational sum-frequency generation (SFG) is used in a wide range of applications where soft matter or solid interfaces are to be probed on a molecular level through their vibrational modes. In recent years, phase-specific sum-frequency generation (PS-SFG, also known as heterodyne-detected SFG) spectroscopy has been increasingly replacing its predecessor (direct SFG, also known as homodyne SFG) as the experimental technique of choice for characterizing interfacial structure. The technique enables phase sensitive measurements, allowing for the determination of the real and imaginary parts of the interfacial vibrational response function and thereby the unambiguous identification of molecular orientation. This phase-sensitivity requires, however, a complete understanding of the complex optical properties of the sample and of their effect on the signal. These optical properties significantly influence the raw spectral data from which the real and imaginary parts of the second-order susceptibility are retrieved. We show that it is essential to correct the data appropriately to infer the true molecular response. The current study presents a detailed description of the physical contributions to the phase-resolved spectrum, allowing a direct comparison between the phase-resolved spectrum and that obtained using the well-understood direct detection method in a step-by-step data analysis process. In addition to phase sensitivity, PS-SFG has been shown to increase the sensitivity compared to traditional (direct) SFG spectroscopy. We present a quantitative comparison between theoretical limits of the signal-to-noise ratio of both techniques, which shows that for many systems the signal-to-noise ratio is very similar for direct- and phase-specific SFG signals. [ABSTRACT FROM AUTHOR]

The energetically unfavorable termination of the hydrogen-bonded network of water molecules at the air/water interface causes molecular rearrangement to minimize the free energy. The long-standing question is how water minimizes the surface free energy. The combination of advanced, surface-specific nonlinear spectroscopy and theoretical simulation provides new insights. The complex χ(2) spectra of isotopically diluted water surfaces obtained by heterodyne-detected sum frequency generation spectroscopy and molecular dynamics simulation show excellent agreement, assuring the validity of the microscopic picture given in the simulation. The present study indicates that there is no ice-like structure at the surface-in other words, there is no increase of tetrahedrally coordinated structure compared to the bulk-but that there are water pairs interacting with a strong hydrogen bond at the outermost surface. Intuitively, this can be considered a consequence of the lack of a hydrogen bond toward the upper gas phase, enhancing the lateral interaction at the boundary. This study also confirms that the major source of the isotope effect on the water χ(2) spectra is the intramolecular anharmonic coupling, i.e., Fermi resonance. [ABSTRACT FROM AUTHOR]

Abstract: We report investigations of the vibrational dynamics of water molecules at the water–air and at the water–lipid interface. Following vibrational excitation with an intense femtosecond infrared pulse resonant with the O–H stretch vibration of water, we follow the subsequent relaxation processes using the surface-specific spectroscopic technique of sum frequency generation. This allows us to selectively follow the vibrational relaxation of the approximately one monolayer of water molecules at the interface. Although the surface vibrational spectra of water at the interface with air and lipids are very similar, we find dramatic variations in both the rates and mechanisms of vibrational relaxation. For water at the water–air interface, very rapid exchange of vibrational energy occurs with water molecules in the bulk, and this intermolecular energy transfer process dominates the response. For membrane-bound water at the lipid interface, intermolecular energy transfer is suppressed, and intramolecular relaxation dominates. The difference in relaxation mechanism can be understood from differences in the local environments experienced by the interfacial water molecules in the two different systems. [Copyright &y& Elsevier]