Hydrogen bonding at the water surface revealed by isotopic dilution spectroscopy.

The air-water interface is perhaps the most common liquid interface. It covers more than 70 per cent of the Earth's surface and strongly affects atmospheric, aerosol and environmental chemistry. The air-water interface has also attracted much interest as a model system that allows rigorous tests of theory, with one fundamental question being just how thin it is. Theoretical studies have suggested a surprisingly short 'healing length' of about 3 ångströms (1 Å = 0.1 nm), with the bulk-phase properties of water recovered within the top few monolayers. However, direct experimental evidence has been elusive owing to the difficulty of depth-profiling the liquid surface on the ångström scale. Most physical, chemical and biological properties of water, such as viscosity, solvation, wetting and the hydrophobic effect, are determined by its hydrogen-bond network. This can be probed by observing the lineshape of the OH-stretch mode, the frequency shift of which is related to the hydrogen-bond strength. Here we report a combined experimental and theoretical study of the air-water interface using surface-selective heterodyne-detected vibrational sum frequency spectroscopy to focus on the 'free OD' transition found only in the topmost water layer. By using deuterated water and isotopic dilution to reveal the vibrational coupling mechanism, we find that the free OD stretch is affected only by intramolecular coupling to the stretching of the other OD group on the same molecule. The other OD stretch frequency indicates the strength of one of the first hydrogen bonds encountered at the surface; this is the donor hydrogen bond of the water molecule straddling the interface, which we find to be only slightly weaker than bulk-phase water hydrogen bonds. We infer from this observation a remarkably fast onset of bulk-phase behaviour on crossing from the air into the water phase.

Temporal effects on spectroscopic line shapes, resolution, and sensitivity of the broad-band sum frequency generation.

Sum frequency generation (SFG) is a surface-selective spectroscopy that provides a wealth of molecular-level information on the structure and dynamics at surfaces and interfaces. This paper addresses the general issue of spectral resolution and sensitivity of the broad-band (BB) SFG that involves a spectrally narrow nonresonant (usually visible) and a BB resonant (usually infrared) laser pulses. We examine how the spectral width and temporal shape of the two pulses, and the time delay between them, relate to the spectroscopic line shape and signal level in the BB-SFG measurement. By combining experimental and model calculations, we show that the best spectral resolution and highest signal level are simultaneously achieved when the nonresonant narrow-band upconversion pulse arrives with a nonzero time delay after the resonant BB pulse. The nonzero time delay partially avoids the linear trade-off of improving spectral resolution at the expense of decreasing signal intensity, which is common in BB-SFG schemes utilizing spectral filtering to produce narrow-band visible pulses.

Heterodyne-detected vibrational sum frequency generation spectroscopy.

We present a new technique of broad-band heterodyne-detected sum frequency generation (HD-SFG) spectroscopy and demonstrate its high sensitivity allowing surface-selective measurements of vibrational spectra at submonolayer surface coverage, as low as a few percent of a monolayer. This was achieved without the help of surface enhancement phenomena, on a transparent dielectric substrate (water), and without introducing fluorescent labels, in fact, without utilizing any electronic resonances. Only the intrinsic vibrational transitions were employed for the detection of the analyte molecules (1-octanol). Unlike conventional (homodyne-detected) SFG spectroscopy, where the signal intensity decreases quadratically with decreasing surface coverage, in HD-SFG, the scaling is linear, and the signal is amplified by interference with a reference beam, significantly improving sensitivity and detection limits. At the same time, HD-SFG provides the phase as well as the amplitude of the signal and thus allows accurate subtraction of the non-resonant background--a common problem for surfaces with low concentrations of analyte molecules (i.e., weak resonant signals).

Phase-stabilized two-dimensional electronic spectroscopy.

Two-dimensional (2D) spectroscopy is a powerful technique to study nuclear and electronic correlations between different transitions or initial and final states. Here we describe in detail our development of inherently phase-stabilized 2D Fourier-transform spectroscopy for electronic transitions. A diffractive-optic setup is used to realize heterodyne-detected femtosecond four-wave mixing in a phase-matched box geometry. Wavelength tunability in the visible range is accomplished by means of a 3 kHz repetition-rate laser system and optical parametric amplification. Nonlinear signals are fully characterized by spectral interferometry. Starting from fundamental principles, we discuss the origin of phase stability and the precise calibration of excitation-pulse time delays using movable glass wedges. Automated subtraction of undesired scattering terms removes experimental artifacts. On the theoretical side, the response-function formalism is extended to describe molecules with three electronic levels, and the shape of 2D spectral features is discussed. As an example for this technique, experimental 2D spectra are shown for the dye molecule Nile Blue in acetonitrile at 595 nm, recorded for a series of population times. Simulations explore the influence of different model parameters and qualitatively reproduce the experimental results. We show that correlations between different electronically excited states can be determined from the spectra. The technique described here can be used to measure the third-order response function of complex systems covering several electronic transitions.