Probing the interfacial structure of aqueous surfactants through helium atom evaporation.

Dissolved helium atoms evaporate from liquids in super-Maxwellian speed distributions because their interactions are too weak to enforce full thermal equilibration at the surface as they are "squeezed" out of solution. The excess speeds of these He atoms reflect their final interactions with solvent and solute molecules at the surfaces of water and other liquids. We extend this observation by monitoring He atom evaporation from salty water solutions coated with surfactants. These surface-active molecules span neutral, anionic, and cationic amphiphiles: butanol, 3-methyl-1-butanol, pentanol, pentanoic acid, pentanoate, tetrabutylammonium, benzyltrimethylammonium, hexyltrimethylammonium, and dodecyltrimethylammonium, each characterized by surface tension measurements. The helium energy distributions, recorded in vacuum using a salty water microjet, reveal a sharp distinction between neutral and ionic surfactant films. Helium atoms evaporate through neutral surfactant monolayers in speed distributions that are similar to a pure hydrocarbon, reflecting the common alkyl chains of both. In contrast, He atoms appear to evaporate through ionic surfactant layers in distributions that are closer to pure salty water. We speculate that the ionic surfactants distribute themselves more loosely and deeply through the top layers of the aqueous solution than do neutral surfactants, with gaps between the surfactants that may be filled with salty water. This difference is supported by prior molecular dynamics simulations and ion scattering measurements of surfactant solutions.

Molecular Insights into Chemical Reactions at Aqueous Aerosol Interfaces.

Atmospheric aerosols facilitate reactions between ambient gases and dissolved species. Here, we review our efforts to interrogate the uptake of these gases and the mechanisms of their reactions both theoretically and experimentally. We highlight the fascinating behavior of N2O5 in solutions ranging from pure water to complex mixtures, chosen because its aerosol-mediated reactions significantly impact global ozone, hydroxyl, and methane concentrations. As a hydrophobic, weakly soluble, and highly reactive species, N2O5 is a sensitive probe of the chemical and physical properties of aerosol interfaces. We employ contemporary theory to disentangle the fate of N2O5 as it approaches pure and salty water, starting with adsorption and ending with hydrolysis to HNO3, chlorination to ClNO2, or evaporation. Flow reactor and gas-liquid scattering experiments probe even greater complexity as added ions, organic molecules, and surfactants alter the interfacial composition and reaction rates. Together, we reveal a new perspective on multiphase chemistry in the atmosphere. Expected final online publication date for the Annual Review of Physical Chemistry, Volume 75 is April 2024. Please see http://www.annualreviews.org/page/journal/pubdates for revised estimates.

Creation and Reaction of Solvated Electrons at and near the Surface of Water.

Solvated electrons (es-) are among nature's most powerful reactants, with over 2600 reactions investigated in bulk water. These electrons can also be created at and near the surface of water by exposing an aqueous microjet in vacuum to gas-phase sodium atoms, which ionize into es- and Na+ within the top few layers. When a reactive surfactant is added to the jet, the surfactant and es- become coreactants localized in the interfacial region. We report the reaction of es- with the surfactant benzyltrimethylammonium in a 6.7 M LiBr/water microjet at 235 K and pH = 2. The reaction intermediates trimethylamine (TMA) and benzyl radical are identified by mass spectrometry after they evaporate from solution into the gas phase. Their detection demonstrates that TMA can escape before it is protonated and benzyl before it combines with itself or a H atom. Diffusion-reaction calculations indicate that es- reacts on average within 20 Å of the surface and perhaps within the surfactant monolayer itself, while unprotonated TMA evaporates from the top 40 Å. The escape depth exceeds 1300 Å for the more slowly reacting benzyl radical. These proof-of-principle experiments establish an approach for exploring the near-interfacial analogues of aqueous bulk-phase radical chemistry through the evaporation of reaction intermediates into the gas phase.

Weak Temperature Dependence of the Relative Rates of Chlorination and Hydrolysis of N2O5 in NaCl-Water Solutions.

We have measured the temperature dependence of the ClNO2 product yield in competition with hydrolysis following N2O5 uptake to aqueous NaCl solutions. For NaCl-D2O solutions spanning 0.0054-0.21 M, the ClNO2 product yield decreases on average by only 4 ± 3% from 5 to 25 °C. Less reproducible measurements at 0.54-2.4 M NaCl also fall within this range. The ratio of the rate constants for chlorination and hydrolysis of N2O5 in D2O is determined on average to be 1150 ± 90 at 25 °C up to 0.21 M NaCl, favoring chlorination. This ratio is observed to decrease significantly at the two highest concentrations. An Arrhenius analysis reveals that the activation energy for hydrolysis is just 3.0 ± 1.5 kJ/mol larger than for chlorination up to 0.21 M, indicating that Cl- and D2O attack on N2O5 has similar energetic barriers despite the differences in charge and complexity of these reactants. In combination with the measured preexponential ratio favoring chlorination of 300-200+400, we conclude that the strong preference of N2O5 to undergo chlorination over hydrolysis is driven by dynamic and entropic, rather than enthalpic, factors. Molecular dynamics simulations elucidate the distinct solvation between strongly hydrated Cl- and the hydrophobically solvated N2O5. Combining this molecular picture with the Arrhenius analysis implicates the role of water in mediating interactions between such distinctly solvated species and suggests a role for diffusion limitations on the chlorination reaction.

Exploring Gas-Liquid Reactions with Microjets: Lessons We Are Learning.

Liquid water is all around us: at the beach, in a cloud, from a faucet, inside a spray tower, covering our lungs. It is fascinating to imagine what happens to a reactive gas molecule as it approaches the surface of water in these examples. Some incoming molecules may first be deflected away after colliding with an evaporating water molecule. Those that do strike surface H2O or other surface species may bounce directly off or become momentarily trapped through hydrogen bonding or other attractive forces. The adsorbed gas molecule can then desorb immediately or instead dissolve, passing through the interfacial region and into the bulk, perhaps diffusing back to the surface and evaporating before reacting. Alternatively, it may react with solute or water molecules in the interfacial or bulk regions, and a reaction intermediate or the final product may then desorb into the gas phase. Building a "blow by blow" picture of these pathways is challenging for vacuum-based techniques because of the high vapor pressure of water. In particular, collisions within the thick vapor cloud created by evaporating molecules just above the surface scramble the trajectories and internal states of the gaseous target molecules, hindering construction of gas-liquid reaction mechanisms at the atomic scale that we strive to map out.The introduction of the microjet in 1988 by Faubel, Schlemmer, and Toennies opened up entirely new possibilities. Their inspired solution seems so simple: narrow the end of a glass tube to a diameter smaller than the mean free path of the vapor molecules and then push the liquid through the tube at speeds of a car on a highway. The narrow liquid stream creates a sparse vapor cloud, with water molecules spaced far enough apart that they and the reactant gases interact, at most, weakly. Experimentalists, however, confront a host of challenges: nozzle clogging, unstable jetting, searching for vacuum-compatible solutions, measuring low signal levels, and teasing out artifacts because the slender jet is the smallest surface in the vacuum chamber. In this Account, we describe lessons that we are learning as we explore gases (DCl, (HCOOH)2, N2O5) reacting with water molecules and solute ions in the near-interfacial region of these fast-flowing aqueous microjets.

The Wisconsin Oscillator: A Low-Cost Circuit for Powering Ion Guides, Funnels, and Traps.

In this work, we present the Wisconsin Oscillator, a small, inexpensive, low-power circuit for powering ion-guiding devices such as multipole ion guides, ion funnels, active ion-mobility devices, and non-mass-selective ion traps. The circuit can be constructed for under $30 and produces two antiphase RF waveforms of up to 250 Vp-p in the high kilohertz to low megahertz range while drawing less than 1 W of power. The output amplitude is determined by a 0-6.5 VDC drive voltage, and voltage amplification is achieved using a resonant LC circuit, negating the need for a large RF transformer. The Wisconsin Oscillator automatically oscillates with maximum amplitude at the resonant frequency defined by the onboard capacitors, inductors, and the capacitive load of the ion-guiding device. We show that our circuit can replace larger and more expensive RF power supplies without degradation of the ion signal and expect this circuit to be of use in miniature and portable mass spectrometers as well as in home-built systems utilizing ion-guiding devices.

Competing Segregation of Br- and Cl- to a Surface Coated with a Cationic Surfactant: Direct Measurements of Ion and Solvent Depth Profiles.

Ion-surface scattering experiments can be used to measure elemental depth profiles on the angstrom scale in complex liquid mixtures. We employ NICISS (neutral impact collision ion scattering spectroscopy) to measure depth profiles of dissolved ions and solvent in liquid glycerol containing the cationic surfactant tetrahexylammonium bromide (THA+/Br-) at 0.013 M and mixtures of NaBr + NaCl at 0.4 M total concentration. The experiments reveal that Br- outcompetes Cl- in its attraction to surface THA+, and that THA+ segregates more extensively when more Br- ions are present. Intriguingly, the depths spanned by THA+, Br-, and Cl- ions generally increase with Br- bulk concentration, expanding from ∼10 to ∼25 Šfor both Br- and Cl- depth profiles. This broadening likely occurs because of an increasing pileup of THA+ ions in a multilayer region that spreads the halide ions over a wider depth. The experiments indicate that cationic surfactants enhance Br- and Cl- concentrations in the surface region far beyond their bulk-phase values, making solutions coated with these surfactants potentially more reactive toward gases that can oxidize the halide ions.

Experimental Depth Profiles of Surfactants, Ions, and Solvent at the Angstrom Scale: Studies of Cationic and Anionic Surfactants and Their Salting Out.

Neutral impact ion scattering spectroscopy (NICISS) is used to measure the depth profiles of ionic surfactants, counterions, and solvent molecules on the angstrom scale. The chosen surfactants are 0.010 m tetrahexylammonium bromide (THA+/Br-) and 0.0050 m sodium dodecyl sulfate (Na+/DS-) in the absence and presence of 0.30 m NaBr in liquid glycerol. NICISS determines the depth profiles of the elements C, O, Na, S, and Br through the loss in energy of 5 keV He atoms that travel into and out of the liquid, which is then converted into depth. In the absence of NaBr, we find that THA+ and its Br- counterion segregate together because of charge attraction, forming a narrow double layer that is 10 Šwide and 150 times more concentrated than in the bulk. With the addition of NaBr, THA+ is "salted out" to the surface, increasing the interfacial Br- concentration by 3-fold and spreading the anions over a ∼30 Šdepth. Added NaBr similarly increases the interfacial concentration of DS- ions and broadens their positions. Conversely, the dissolved Br- ions are significantly depleted over a depth of 0-40 Šfrom the surface because of charge repulsion from DS- ions within the interfacial region. These different interfacial Br- propensities correlate with previously measured gas-liquid reactivities: gaseous Cl2 readily reacts with Br- ions in the presence of THA+ but drops 70-fold in the presence of DS-, demonstrating that surfactant headgroup charge controls the reactivity of Br- through changes in its depth profile.

SN2 Reactions of N2O5 with Ions in Water: Microscopic Mechanisms, Intermediates, and Products.

Reactions of dinitrogen pentoxide (N2O5) greatly affect the concentrations of NO3, ozone, OH radicals, methane, and more. In this work, we employ ab initio molecular dynamics and other tools of computational chemistry to explore reactions of N2O5 with anions hydrated by 12 water molecules to shed light on this important class of reactions. The ions investigated are Cl-, SO42-, ClO4-, and RCOO- (R = H, CH3, C2H5). The following main results are obtained: (i) all the reactions take place by an SN2-type mechanism, with a transition state that involves a contact ion pair (NO2+NO3-) that interacts strongly with water molecules. (ii) Reactions of a solvent-separated nitronium ion (NO2+) are not observed in any of the cases. (iii) An explanation is provided for the suppression of ClNO2 formation from N2O5 reacting with salty water when sulfate or acetate ions are present, as found in recent experiments. (iv) Formation of novel intermediate species, such as (SO4NO2-) and RCOONO2, in these reactions is predicted. The results suggest atomistic-level mechanisms for the reactions studied and may be useful for the development of improved modeling of reaction kinetics in aerosol particles.

Production of Br2 from N2O5 and Br- in Salty and Surfactant-Coated Water Microjets.

Gas-liquid scattering experiments are used to investigate the oxidation-reduction reaction N2O5(g) + 2Br-(aq) → Br2(g) + NO3-(aq) + NO2-(aq), a model for the nighttime absorption of N2O5 into aerosol droplets containing halide ions. The detection of evaporating Br2 molecules provides our first observation of a gaseous reaction product generated by a water microjet in vacuum. N2O5 molecules are directed at a 35 µm diameter jet of 6 or 8 m LiBr in water at 263 or 240 K, followed by detection of both unreacted N2O5 and product Br2 molecules by velocity-resolved mass spectrometry. The N2O5 reaction probability at near-thermal collision energy is too small to be measured and likely lies below 0.2. However, the evaporating Br2 product can be detected and controlled by the presence of surfactants. The addition of 0.02 m 1-butanol, which creates ∼40% of a compact monolayer, reduces Br2 production by 35%. Following earlier studies, this reduction may be attributed to surface butanol molecules that block N2O5 entry or alter the near-surface distribution of Br-. Remarkably, addition of the cationic surfactant tetrabutylammonium bromide (TBABr) at 0.005 m (9% of a monolayer) reduces the Br2 signal by 85%, and a 0.050 m solution (58% of a monolayer) causes the Br2 signal to disappear entirely. A detailed analysis suggests that TBA+ efficiently suppresses Br2 evaporation because it tightly bonds to the Br3- intermediate formed in the highly concentrated Br- solution and thereby hinders the rapid release and evaporation of Br2.

Ab initio molecular dynamics studies of formic acid dimer colliding with liquid water.

Ab initio molecular dynamics simulations of formic acid (FA) dimer colliding with liquid water at 300 K have been performed using density functional theory. The two energetically lowest FA dimer isomers were collided with a water slab at thermal and high kinetic energies up to 68kBT. Our simulations agree with recent experimental observations of nearly a complete uptake of gas-phase FA dimer: the calculated average kinetic energy of the dimers immediately after collision is 5 ± 4% of the incoming kinetic energy, which compares well with the experimental value of 10%. Simulations support the experimental observation of no delayed desorption of FA dimers following initial adsorption. Our analysis shows that the FA dimer forms hydrogen bonds with surface water molecules, where the hydrogen bond order depends on the dimer structure, such that the most stable isomer possesses fewer FA-water hydrogen bonds than the higher energy isomer. Nevertheless, even the most stable isomer can attach to the surface through one hydrogen bond despite its reduced hydrophilicity. Our simulations further show that the probability of FA dimer dissociation is increased by high collision energies, the dimer undergoes isomerization from the higher energy to the lowest energy isomer, and concerted double-proton transfer occurs between the FA monomers. Interestingly, proton transfer appears to be driven by the release of energy arising from such isomerization, which stimulates those internal vibrational degrees of freedom that overcome the barrier of a proton transfer.

Control of Interfacial Cl2 and N2O5 Reactivity by a Zwitterionic Phospholipid in Comparison with Ionic and Uncharged Surfactants.

Gas-liquid scattering experiments reveal that charge-separated but neutral (zwitterionic) surfactants catalyze the oxidation of dissolved Br- to Br2 by gaseous Cl2 at the surface of a 0.3 M NaBr/glycerol solution. Solutions of NaBr dissolved in glycerol with no surfactant were compared with solutions coated with zwitterionic, cationic, and anionic surfactants at dilute surface concentrations of 1.1 to 1.5 × 1014 cm-2 (less than 65% of maximum chain packing). The zwitterionic phospholipid enhances Cl2 conversion of Br- to Br2 by a factor of 1.61 ± 0.15, in comparison with a 14-fold enhancement by a cationic surfactant (tetrahexylammonium) and a five-fold suppression by an anionic surfactant (dodecyl sulfate). Further studies indicate that even an uncharged surfactant, monododecanoylglycerol, enhances Cl2 → Br2 production. Similar behavior is observed for the oxidation of Br- to Br2 by N2O5; it is just slightly suppressed by the phospholipid and strongly enhanced by the cationic surfactant. Collectively, these results suggest that attractions and repulsions between the negative Br- ions and the positive and negative charges of the surfactant headgroups draw Br- ions to the surface or repel them away. At low coverages, ion-induced dipole and dispersion interactions between the CH2 groups and Br- or Cl2 may also enhance reactivity. These results demonstrate that the hydrocarbon chains of loosely packed surfactants do not necessarily block gas-liquid reactions but that positively charged, and even uncharged, groups can instead facilitate reactions by bringing gas-phase and solution-phase reagents together in the interfacial region.

N2O5 at water surfaces: binding forces, charge separation, energy accommodation and atmospheric implications.

Interactions of N2O5 with water media are of great importance in atmospheric chemistry and have been the topic of extensive research for over two decades. Nevertheless, many physical and chemical properties of N2O5 at the surface or in bulk water are unknown or not microscopically understood. This study presents extensive new results on the physical properties of N2O5 in water and at the surface of water, with a focus on their microscopic basis. The main results are obtained using ab initio molecular dynamics and calculations of a potential of mean force. These include: (1) collisions of N2O5 with water at 300 K lead to trapping at the surface for at least 20 ps and with 95% probability. (2) During that time, there is no N2O5 hydrolysis, evaporation, or entry into the bulk. (3) Charge separation between the NO2 and NO3 groups of N2O5, fluctuates significantly with time. (4) Energy accommodation of the colliding N2O5 at the surface takes place within picoseconds. (5) The binding energy of N2O5 to a nanosize amorphous ice particle at 0 K is on the order of 15 kcal mol-1 for the main surface site. N2O5 binding to the cluster is due to one weak hydrogen bond and to interactions between partial charges on the N2O5 and on water. (6) The free-energy profile was calculated for transporting N2O5 from the gas phase through the interface and into bulk water. The corresponding concentration profile exhibits a propensity for N2O5 at the aqueous surface. The free energy barrier for entry from the surface into the bulk was determined to be 1.8 kcal mol-1. These findings are used to interpret recent experiments. We conclude with implications of this study for atmospheric chemistry.

Reactions of N2O5 with Salty and Surfactant-Coated Glycerol: Interfacial Conversion of Br- to Br2 Mediated by Alkylammonium Cations.

Gas-liquid scattering and product-yield experiments are used to investigate reactions of N2O5 with glycerol containing Br- and surfactant ions. N2O5 oxidizes Br- to Br2 for every solution tested: 2.7 M NaBr, 0.03 M tetrahexylammonium bromide (THABr), 0.03 M THABr + 0.5 M NaBr, 0.03 M THABr + 0.5 M NaCl, 0.03 M THABr + 0.01 M sodium dodecyl sulfate (SDS), and 0.01 M cetyltrimethylammonium bromide (CTABr). N2O5 also reacts with glycerol itself to produce mono- and dinitroglycerin. Surface tension measurements indicate that 0.03 M THABr and 2.7 M NaBr have similar interfacial Br- concentrations, though their bulk Br- concentrations differ by 90-fold. We find that twice as much Br2 is produced in the presence of THA+, implying that the conversion of Br- to Br2 is initiated at the interface, perhaps mediated by the charged, hydrophobic pocket within the surface THA+ cation. The addition of 0.5 M NaBr, 0.5 M NaCl, or 0.01 M SDS to 0.03 M THABr lowers the Br2 production rate by 23%, 63%, and 67% of the THABr value, respectively. When CTA+ is substituted for THA+, Br2 production drops to 12% of the THABr value. The generation of Br2 under such different conditions implies that trace amounts of surface-active alkylammonium ions can catalyze interfacial N2O5 reactions, even when salts and other surfactants are present.

Deprotonation of formic acid in collisions with a liquid water surface studied by molecular dynamics and metadynamics simulations.

Deprotonation of organic acids at aqueous surfaces has important implications in atmospheric chemistry and other disciplines, yet it is not well-characterized or understood. This article explores the interactions of formic acid (FA), including ionization, in collisions at the air-water interface. Ab initio molecular dynamics simulations with dispersion-corrected density functional theory were used. The 8-50 picosecond duration trajectories all resulted in the adsorption of FA within the interfacial region, with no scattering, absorption into the bulk or desorption into the vapor. Despite the known weak acidity of FA, spontaneous deprotonation of the acid was observed at the interface on a broad picosecond timescale, ranging from a few picoseconds typical for stronger acids to tens of picoseconds. Deprotonation occurred in 4% of the trajectories, and was followed by Grotthuss proton transfer through adjacent water molecules. Both sequential and ultrafast concerted proton transfer were observed. The formation of contact ion pairs and solvent-separated ion pairs, and finally the reformation of neutral FA, both trans and cis conformers, occurred in different stages of the dynamics. To better understand the deprotonation mechanisms at the interface compared with the process in bulk water, we used well-tempered metadynamics to obtain deprotonation free energy profiles. While in bulk water FA deprotonation has a free energy barrier of 14.8 kJ mol-1, in fair agreement with the earlier work, the barrier at the interface is only 7.5 kJ mol-1. Thus, at the air-water interface, FA may dissociate more rapidly than in the bulk. This finding can be rationalized with reference to the dissimilar aqueous solvation and hydrogen-bonding environments in the interface compared to those in bulk liquid water.

Microjets and coated wheels: versatile tools for exploring collisions and reactions at gas-liquid interfaces.

This tutorial review describes experimental aspects of two techniques for investigating collisions and reactions at the surfaces of liquids in vacuum. These gas-liquid scattering experiments provide insights into the dynamics of interfacial processes while minimizing interference from vapor-phase collisions. We begin with a historical survey and then compare attributes of the microjet and coated-wheel techniques, developed by Manfred Faubel and John Fenn, respectively, for studies of high- and low-vapor pressure liquids in vacuum. Our objective is to highlight the strengths and shortcomings of each technique and summarize lessons we have learned in using them for scattering and evaporation experiments. We conclude by describing recent microjet studies of energy transfer between O2 and liquid hydrocarbons, HCl dissociation in salty water, and super-Maxwellian helium evaporation.

Gas-Microjet Reactive Scattering: Collisions of HCl and DCl with Cool Salty Water.

Liquid microjets provide a powerful means to investigate reactions of gases with salty water in vacuum while minimizing gas-vapor collisions. We use this technique to explore the fate of gaseous HCl and DCl molecules impinging on 8 molal LiCl and LiBr solutions at 238 K. The experiments reveal that HCl or DCl evaporate infrequently if they become thermally accommodated at the surface of either solution. In particular, we observe minimal thermal desorption of HCl following HCl collisions and no distinct evidence for rapid, interfacial DCl→HCl exchange following DCl collisions. These results imply that surface thermal motions are not generally strong enough to propel momentarily trapped HCl or DCl back into the gas phase before they ionize and disappear into solution. Instead, only HCl and DCl molecules that scatter directly from the surface escape entry. These recoiling molecules transfer less energy upon collision to LiBr/H2O than to LiCl/H2O, reflecting the heavier mass of Br(-) than of Cl(-) in the interfacial region.

Super-Maxwellian helium evaporation from pure and salty water.

Helium atoms evaporate from pure water and salty solutions in super-Maxwellian speed distributions, as observed experimentally and modeled theoretically. The experiments are performed by monitoring the velocities of dissolved He atoms that evaporate from microjets of pure water at 252 K and 4-8.5 molal LiCl and LiBr at 232-252 K. The average He atom energies exceed the flux-weighted Maxwell-Boltzmann average of 2RT by 30% for pure water and 70% for 8.5m LiBr. Classical molecular dynamics simulations closely reproduce the observed speed distributions and provide microscopic insight into the forces that eject the He atoms from solution. Comparisons of the density profile and He kinetic energies across the water-vacuum interface indicate that the He atoms are accelerated by He-water collisions within the top 1-2 layers of the liquid. We also find that the average He atom kinetic energy scales with the free energy of solvation of this sparingly soluble gas. This free-energy difference reflects the steeply decreasing potential of mean force on the He atoms in the interfacial region, whose gradient is the repulsive force that tends to expel the atoms. The accompanying sharp decrease in water density suppresses the He-water collisions that would otherwise maintain a Maxwell-Boltzmann distribution, allowing the He atom to escape at high energies. Helium is especially affected by this reduction in collisions because its weak interactions make energy transfer inefficient.

DCl Transport through Dodecyl Sulfate Films on Salty Glycerol: Effects of Seawater Ions on Gas Entry.

Gas-liquid scattering experiments were employed to measure the entry and dissociation of the acidic gas DCl into salty glycerol coated with dodecyl sulfate ions (DS(-) = CH3(CH2)11OSO3(-)). Five sets of salty solutions were examined: 0.25 and 0.5 M NaCl, 0.25 M MgCl2, 0.25 M CaCl2, and artificial sea salt. DS(-) bulk concentrations were varied from 0 to 11 mM, generating DS(-) surface coverages of up to 34% of a compact monolayer, as determined by surface tension and argon scattering measurements. DS(-) surface segregation is enhanced by the dissolved salts in the order MgCl2 ≈ CaCl2 > sea salt > NaCl. We find that DCl penetration through the dodecyl chains decreases at first gradually and then sharply as more chains segregate to the surface, dropping from 70% entry on bare glycerol to 11% for DS(-) surface concentrations of 1.8 × 10(14) cm(-2). When plotted against DS(-) surface concentration, the DCl entry probabilities fall within a single band for all solutions. These observations imply that the monovalent Na(+) and divalent Ca(2+) and Mg(2+) ions do not bind differently enough to the ROSO3(-) headgroup to significantly alter the diffusive passage of DCl molecules through the dodecyl chains at the same DS(-) chain density. The chief difference among the salts is the greater propensity for the divalent salts to expel the soluble ionic surfactant to the surface.

Selective photoelectrochemical reduction of aqueous CO2 to CO by solvated electrons.

Reduction of CO2 by direct one-electron activation is extraordinarily difficult because of the -1.9 V reduction potential of CO2. Demonstrated herein is reduction of aqueous CO2 to CO with greater than 90% product selectivity by direct one-electron reduction to CO2(˙-) by solvated electrons. Illumination of inexpensive diamond substrates with UV light leads to the emission of electrons directly into water, where they form solvated electrons and induce reduction of CO2 to CO2(˙-). Studies using diamond were supported by studies using aqueous iodide ion (I(-)), a chemical source of solvated electrons. Both sources produced CO with high selectivity and minimal formation of H2 . The ability to initiate reduction reactions by emitting electrons directly into solution without surface adsorption enables new pathways which are not accessible using conventional electrochemical or photochemical processes.