Champika N. Weeraman

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.

Specific Cation Effects on the Bimodal Acid–Base Behavior of the Silica/Water Interface

Using nonresonant second harmonic generation spectroscopy, we have monitored the change in surface charge density of the silica/water interface over a broad pH range in the presence of different alkali chlorides. Planar silica is known to possess two types of surface sites with pKa values of ∼4 and ∼9, which are attributed to different solvation environments of the silanols. We report that varying the alkali chloride electrolyte significantly changes the effective acid dissociation constant (pKa(eff)) for the less acidic silanol groups, with the silica/NaClaq and silica/CsClaq interfaces exhibiting the lowest and highest pKa(eff) values of 8.3(1) and 10.8(1), respectively. Additionally, the relative populations of the two silanol groups are also very sensitive to the electrolyte identity. The greatest percentage of acidic silanol groups was 60(2)% for the silica/LiClaq interface in contrast to the lowest value of 20(2)% for the silica/NaClaq interface. We attribute these changes in the bimodal behavior to the influence of alkali ions on the interfacial water structure and its corresponding effect on surface acidity.

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.

Rubbing-induced anisotropy of long alkyl side chains at polyimide surfaces

Molecular organization at polyimide surfaces used as alignment layers in liquid crystal displays was investigated using vibrational sum frequency generation (SFG) spectroscopy. We focus on the orientation of the long alkyl side groups at the polymer surface using polarization-selected SFG spectra of the CH(3)- and CH(2)-stretch modes of the side chain. Mechanical rubbing and baking, an accepted industrial procedure used to produce pretilt of the liquid crystal, was found to induce pronounced azimuthal anisotropy in the orientational distribution of the alkyl side chains. Orientational analysis of the SFG vibrational spectra in terms of the azimuthal and tilt angles (in and out of plane, respectively) of the alkyl side chains shows their preferential tilt along the rubbing direction, with the azimuthal distribution narrower for stronger rubbed polymer samples.

Following the Azide‐Alkyne Cycloaddition at the Silica/Solvent Interface with Sum Frequency Generation

The Cu(I) -catalyzed 1,3-dipolar azide-alkyne cycloaddition (CuAAC) has arisen as one of the most useful chemical transformations for introducing complexity onto surfaces and materials owing to its functional-group tolerance and high yield. However, methods for monitoring such reactions in situ at the widely used silica/solvent interface are hampered by challenges associated with probing such buried interfaces. Using the surface-specific technique broadband sum frequency generation (SFG), we monitored the reaction of a benzyl azide monolayer in real time at the silica/methanol interface. A strong peak at 2096 cm(-1) assigned to the azides was observed for the first time by SFG. Using a cyano-substituted alkyne, the decrease of the azide peak and the increase of the cyano peak (2234 cm(-1) ) were probed simultaneously. From the kinetic analysis, the reaction order with respect to copper was determined to be 2.1, suggesting that CuAAC on the surface follows a similar mechanism as in solution.

Sum frequency generation from alkanethiol capped metallic nanoparticles and vibrational mode specific enhancement in nanoparticle aggregates

Vibrational Sum Frequency Generation (VSFG) on gold and silver nanoparticles capped with alkanethiols is studied. Aggregation of nanoparticles is characterized using TEM and SEM methods. VSFG process is enhanced due to the coupling of surface plasmon induced by the visible radiation in gold nanoparticle with vibrational transition of chemisorbed alkanethiol excited by the infrared beam. VSFG spectra show methyl and methylene stretch transitions. The ratio of their intensities varies with changing size of the particles and length of alkane chain. Dramatic change in intensity ratio and overall enhancement of VSFG intensity is observed when aggregation of gold nanoparticles occurs. For the first time we report the mode-specific SFG enhancement, namely, the methyl antisymmetric stretch gains the highest intensity. One possible explanation is that enhancement is caused by the change in SFG selection rules due to the effect of locally inhomogeneous electric field of plasmon. VSFG response from aggregates is significantly depolarized in comparison with response from non-interacting particles. This can be due to the depolarization of plasmon induced in aggregates of metallic nanoparticles. Divergence of VSFG beam from aggregates is stronger than that of the beam from non-interacting particles. This can be attributed to the incoherent nonlinear scattering in aggregates due to depolarization of surface plasmon. Potential applications of SFG nanoprobes for imaging, IR radiation conversion, and opto-electronic integrated circuits are discussed.