Direct Evidence for a Surface and Bulk Specific Response in the Sum-Frequency Generation Spectrum of the Water Bend Vibration

Spectroscopic studies of aqueous surfaces can provide a fundamental understanding of interfacial processes. These studies have largely focused on the OH stretch vibrations of water, which is unfortunate as the bending mode is an attractive feature to probe as it is relatively free of inter- and intramolecular couplings. However, the origin of the response of the bending mode is highly debated and has been assigned to either surface-specific or to bulk effects. Here, we study the bending mode of pure water and charged aqueous surfaces using heterodyne-detected vibrational sum frequency generation spectroscopy (HD-VSFG) to quantify the two effects. Our results show a low - (1626 cm-1) and a high - (1656 cm-1) frequency component which can be unambiguously assigned to an interfacial dipole and a bulk quadrupolar response, respectively. We thus demonstrate that probing the bending mode provides structural and quantitative information on both the surface and the bulk.

Vibrational exciton delocalization precludes the use of infrared intensities as proxies for surfactant accumulation on aqueous surfaces

Surface-sensitive vibrational spectroscopy is a common tool for measuring molecular organization and intermolecular interactions at interfaces. Peak intensity ratios are typically used to extract molecular information from one-dimensional spectra but...

Detecting Intermediates and Products of Fast Heterogeneous Reactions on Liquid Surfaces via Online Mass Spectrometry

One of the research priorities in atmospheric chemistry is to advance our understanding of heterogeneous reactions and their effect on the composition of the troposphere. Chemistry on aqueous surfaces is particularly important because of their ubiquity and expanse. They range from the surfaces of oceans (360 million km2), cloud and aerosol drops (estimated at ~10 trillion km2) to the fluid lining the human lung (~150 m2). Typically, ambient air contains reactive gases that may affect human health, influence climate and participate in biogeochemical cycles. Despite their importance, atmospheric reactions between gases and solutes on aqueous surfaces are not well understood and, as a result, generally overlooked. New, surface-specific techniques are required that detect and identify the intermediates and products of such reactions as they happen on liquids. This is a tall order because genuine interfacial reactions are faster than mass diffusion into bulk liquids, and may produce novel species in low concentrations. Herein, we review evidence that validates online pneumatic ionization mass spectrometry of liquid microjets exposed to reactive gases as a technique that meets such requirements. Next, we call attention to results obtained by this approach on reactions of gas-phase ozone, nitrogen dioxide and hydroxyl radicals with various solutes on aqueous surfaces. The overarching conclusion is that the outermost layers of aqueous solutions are unique media, where most equilibria shift and reactions usually proceed along new pathways, and generally faster than in bulk water. That the rates and mechanisms of reactions at air-aqueous interfaces may be different from those in bulk water opens new conceptual frameworks and lines of research, and adds a missing dimension to atmospheric chemistry.

Detecting Intermediates and Products of Fast Heterogeneous Reactions on Liquid Surfaces via Online Mass Spectrometry

One of the research priorities in atmospheric chemistry is to advance our understanding of heterogeneous reactions and their effect on the composition of the troposphere. Chemistry on aqueous surfaces is particularly important in this regard because of their ubiquity and expanse. They range from the surfaces of oceans (360 million km2), cloud and aerosol drops (~10 trillion km2) to the fluids lining the human lung (~200 m2). Typically, ambient air contains reactive gases that may affect human health, influence climate and participate in biogeochemical cycles. Despite their importance, reactions between gases and solutes at air-aqueous interfaces are not well understood. New, surface-specific techniques are required that detect and identify the intermediates and products of such reactions as they happen on liquids. This is a tall order because genuine interfacial reactions are faster than mass diffusion into bulk liquids, and may produce novel species at low concentrations. Herein, we review evidence that validates online pneumatic ionization mass spectrometry of liquid microjets dosed by reactive gases as a technique meeting such requirements. Next, we call attention to results obtained by this approach on reactions of ozone, nitrogen dioxide and hydroxyl radicals with various solutes on aqueous surfaces. The overarching conclusion is that the outermost layers of aqueous solutions are unique media, where equilibria shift and reactions proceed faster than, in some cases along different pathways from the bulk liquids. The fact that the rates and mechanisms of reactions at air-aqueous interfaces may not be deduced from experiments in bulk liquids opens new conceptual frameworks and lines of research, and adds an overlooked dimension to atmospheric chemistry.