A Detailed Reaction Mechanism for Thiosulfate Oxidation by Ozone in Aqueous Environments.

The ozone oxidation, or ozonation, of thiosulfate is an important reaction for wastewater processing, where it is used for remediation of mining effluents, and for studying aerosol chemistry, where its fast reaction rate makes it an excellent model reaction. Although thiosulfate ozonation has been studied since the 1950s, challenges remain in developing a realistic reaction mechanism that can satisfactorily account for all observed products with a sequence of elementary reaction steps. Here, we present novel measurements using trapped microdroplets to study the pH-dependent thiosulfate ozonation kinetics.

Time-Resolved X-ray Emission Spectroscopy and Resonant Inelastic X-ray Scattering Spectroscopy of Laser Irradiated Carbon.

The existence of liquid carbon as an intermediate phase preceding the formation of novel carbon materials has been a point of contention for several decades. Experimental observation of such a liquid state requires nonthermal melting of solid carbon materials at various laser fluences and pulse properties. Reflectivity experiments performed in the mid-1980s reached opposing conclusions regarding the metallic or insulating properties of the purported liquid state.

Spiers Memorial Lecture: Water at interfaces.

In this article we discuss current issues in the context of the four chosen subtopics for the meeting: dynamics and nano-rheology of interfacial water, electrified/charged aqueous interfaces, ice interfaces, and soft matter/water interfaces. We emphasize current advances in both theory and experiment, as well as important practical manifestations and areas of unresolved controversy.

Agglomeration Drives the Reversed Fractionation of Aqueous Carbonate and Bicarbonate at the Air-Water Interface.

In the course of our investigations of the adsorption of ions to the air-water interface, we previously reported the surprising result that doubly charged carbonate anions exhibit a stronger surface affinity than singly charged bicarbonate anions. In contrast to monovalent, weakly hydrated anions, which generally show enhanced concentrations in the interfacial region, multivalent (and strongly hydrated) anions are expected to show a much weaker surface propensity. In the present work, we use resonantly enhanced deep-UV second-harmonic generation spectroscopy to measure the Gibbs free energy of adsorption of both carbonate (CO) and bicarbonate (HCO) anions to the air-water interface.

On the mechanisms of ion adsorption to aqueous interfaces: air-water vs. oil-water.

The adsorption of ions to water-hydrophobe interfaces influences a wide range of phenomena, including chemical reaction rates, ion transport across biological membranes, and electrochemical and many catalytic processes; hence, developing a detailed understanding of the behavior of ions at water-hydrophobe interfaces is of central interest. Here, we characterize the adsorption of the chaotropic thiocyanate anion (SCN) to two prototypical liquid hydrophobic surfaces, water-toluene and water-decane, by surface-sensitive nonlinear spectroscopy and compare the results against our previous studies of SCN adsorption to the air-water interface. For these systems, we observe no spectral shift in the charge transfer to solvent spectrum of SCN, and the Gibb's free energies of adsorption for these three different interfaces all agree within error.

Saturable Absorption of Free-Electron Laser Radiation by Graphite near the Carbon K-Edge.

The interaction of intense light with matter gives rise to competing nonlinear responses that can dynamically change material properties. Prominent examples are saturable absorption (SA) and two-photon absorption (TPA), which dynamically increase and decrease the transmission of a sample depending on pulse intensity, respectively. The availability of intense soft X-ray pulses from free-electron lasers (FELs) has led to observations of SA and TPA in separate experiments, leaving open questions about the possible interplay between and relative strength of the two phenomena.

Characterizing Anion Adsorption to Aqueous Interfaces: Toluene-Water versus Air-Water.

We continue our investigation of the behavior of simple ions at aqueous interfaces, employing the combination of two surface-sensitive nonlinear spectroscopy tools, broadband deep UV electronic sum-frequency generation and UV second harmonic generation, to characterize the adsorption of thiocyanate to the interface of water with toluene─a prototypical hydrophobe. We find that both the interfacial spectrum and the Gibbs free energy of adsorption closely match results previously reported for the air-water interface. We observe no relative spectral shift in the higher-energy CTTS transition of thiocyanate, implying similar solvation environments for the two interfaces.

Angstrom-Resolved Interfacial Structure in Buried Organic-Inorganic Junctions.

Charge transport processes at interfaces play a crucial role in many processes. Here, the first soft x-ray second harmonic generation (SXR SHG) interfacial spectrum of a buried interface (boron-Parylene N) is reported. SXR SHG shows distinct spectral features that are not observed in x-ray absorption spectra, demonstrating its extraordinary interfacial sensitivity.

Molecular Properties and Chemical Transformations Near Interfaces.

The properties of bulk water and aqueous solutions are known to change in the vicinity of an interface and/or in a confined environment, including the thermodynamics of ion selectivity at interfaces, transition states and pathways of chemical reactions, and nucleation events and phase growth. Here we describe joint progress in identifying unifying concepts about how air, liquid, and solid interfaces can alter molecular properties and chemical reactivity compared to bulk water and multicomponent solutions. We also discuss progress made in interfacial chemistry through advancements in new theory, molecular simulation, and experiments.

Rydberg States of H and HeH as Potential Coolants for Primordial Star Formation.

Current theory and measurements establish the age of the universe as ca. 13.8 billion years.

Catalytic Mechanism of Interfacial Water in the Cycloaddition of Quadricyclane and Diethyl Azodicarboxylate.

"On-water" catalysis, the unusual activity of water molecules at the organic solvent-water interface, has been demonstrated in many organic reactions. However, the catalytic mechanism has remained unclear, largely because of the irreproducibility of the organic-water interface under the common stirring condition. Here, the interfacial area was controlled by employing adsorbed water on mesoporous silica nanoparticles as the catalyst.

New Insights into the Charge-Transfer-to-Solvent Spectrum of Aqueous Iodide: Surface versus Bulk.

Liquid phase charge-transfer-to-solvent (CTTS) transitions are important, as they serve as photochemical routes to solvated electrons. In this work, broadband deep-ultraviolet electronic sum frequency generation (DUV-ESFG) and two-photon absorption (2PA) spectroscopic techniques were used to assign and compare the nature of the aqueous iodide CTTS excitations at the air/water interface and in bulk solution. In the one-photon absorption (1PA) spectrum, excitation to the 6s Rydberg-like orbital (5p → 6s) gives rise to a pair of spin-orbit split iodine states, P and P.

Terahertz VRT Spectroscopy of the Water Hexamer-h12 Cage: Dramatic Libration-Induced Enhancement of Hydrogen Bond Tunneling Dynamics.

We report the assignment and analysis of 176 transitions belonging to a librational band of the (HO) cage isomer near 525 cm(15 THz). From a fit of the transitions to an asymmetric top model, we observe both dramatic changes in the rotational constants relative to the ground state, indicating significant nonrigidity, and striking enhancement in the tunneling motions that break and reform the hydrogen bonds in the cluster. This is the fifth water cluster system to display such an enhancement in the 15 THz librational region, the details of which may help to elucidate the hydrogen bond dynamics occurring in bulk liquid water.

Charge-Transfer-to-Solvent Spectrum of Thiocyanate at the Air/Water Interface Measured by Broadband Deep Ultraviolet Electronic Sum Frequency Generation Spectroscopy.

Measurement of interfacial electronic spectra is a powerful tool for characterizing the properties of ions in physical, biological, environmental, and industrial systems. Here, we describe measurement of the complete charge-transfer-to-solvent (CTTS) spectrum of thiocyanate at the air/water interface using our recently developed femtosecond broadband deep ultraviolet electronic sum frequency generation technique. We find that the lower energy CTTS band characterized in bulk thiocyanate spectra is not observed in the | χ|-power spectrum of the air/water interface, likely reflecting the different solvation environments, altering of the charge distribution of the ion, and possible ion-ion effects, and that sodium and potassium salts yield identical spectra.

Soft X-ray Absorption Spectroscopy of Liquids and Solutions.

X-ray absorption spectroscopy (XAS) is an electronic absorption technique for which the initial state is a deeply buried core level. The photon energies corresponding to such transitions are governed primarily by the binding energies of the initial state. Because the binding energies of core electrons vary significantly among atomic species, this makes XAS an element-selective spectroscopy.

Mechanism of ion adsorption to aqueous interfaces: Graphene/water vs. air/water.

The adsorption of ions to aqueous interfaces is a phenomenon that profoundly influences vital processes in many areas of science, including biology, atmospheric chemistry, electrical energy storage, and water process engineering. Although classical electrostatics theory predicts that ions are repelled from water/hydrophobe (e.g.

Hydrogen bond network rearrangement dynamics in water clusters: Effects of intermolecular vibrational excitation on tunneling rates.

Theoretical studies of hydrogen bond network rearrangement (HBNR) dynamics in liquid water have indicated that librational motions initiate the hydrogen bond breaking/formation processes. We present the results of using a simple time evolution method to extract and compare the tunneling lifetimes for motions that break and reform the hydrogen bond for the water dimer, trimer, and pentamer from the experimentally measured tunneling splittings in the ground and excited intermolecular vibrational states. We find that the specific nature of the intermolecular vibrational excitation does not significantly influence the tunneling lifetime of the dimer, but that only excitations to a librational vibration affect the water trimer and pentamer lifetimes.

Hydrogen bond breaking dynamics in the water pentamer: Terahertz VRT spectroscopy of a 20 μm libration.

Hydrogen bonds in solid and liquid water are formed and broken via librational vibrations, hence characterizing the details of these motions is vital to understanding these important dynamics. Here we report the measurement and assignment of 875 transitions comprising 6 subbands originating from out-of-plane librational transitions of the water pentamer-d near 512 cm. The precisely measured (ca.

Broadband Deep UV Spectra of Interfacial Aqueous Iodide.

The behavior of ions at aqueous interfaces influences vital processes in many fields but has long remained a subject of controversy. Over the past decade, counterintuitive surface concentration enhancement of several ions in aqueous solution has been demonstrated via nonlinear laser spectroscopy and mass spectrometry. While the evidence for significant ion enhancement at the air-water interface is convincing, the mechanism remains incompletely understood.

Structure and torsional dynamics of the water octamer from THz laser spectroscopy near 215 μm.

Clusters of eight water molecules play an important role in theoretical analysis of aqueous structure and dynamics but have proven to be challenging experimental targets. Here we report the high-resolution spectroscopic characterization of the water octamer. Terahertz (THz) vibration-rotation-tunneling (VRT) spectroscopy resolved 99 transitions with 1 part per million precision in a narrow range near 46.

Communication: Hydrogen bonding interactions in water-alcohol mixtures from X-ray absorption spectroscopy.

While methanol and ethanol are macroscopically miscible with water, their mixtures exhibit negative excess entropies of mixing. Despite considerable effort in both experiment and theory, there remains significant disagreement regarding the origin of this effect. Different models for the liquid mixture structure have been proposed to address this behavior, including the enhancement of the water hydrogen bonding network around the alcohol hydrophobic groups and microscopic immiscibility or clustering.

Far-infrared VRT spectroscopy of the water dimer: Characterization of the 20 μm out-of-plane librational vibration.

We report the first high-resolution spectra for the out-of-plane librational vibration in the water dimer. Three vibrational subbands comprising a total of 188 transitions have been measured by diode laser spectroscopy near 500 cm(-1) and assigned to (H2O)2 libration-rotation-tunneling eigenstates. The band origin for the Ka = 1 subband is ~524 cm(-1).

Properties of aqueous nitrate and nitrite from x-ray absorption spectroscopy.

Nitrate and nitrite ions are of considerable interest, both for their widespread use in commercial and research contexts and because of their central role in the global nitrogen cycle. The chemistry of atmospheric aerosols, wherein nitrate is abundant, has been found to depend on the interfacial behavior of ionic species. The interfacial behavior of ions is determined largely by their hydration properties; consequently, the study of the hydration and interfacial behavior of nitrate and nitrite comprises a significant field of study.