Atmospheric Intermediates at the Air-Water Interface.

The air-water interface (AWI) is a ubiquitous reaction field different from the bulk phase where unexpected reactions and physical processes often occur. The AWI is a region where air contacts cloud droplets, aerosol particles, the ocean surface, and biological surfaces such as fluids that line human epithelia. In Earth's atmosphere, short-lived intermediates are expected to be generated at the AWI during multiphase reactions. Recent experimental developments have enabled the direct detection of atmospherically relevant, short-lived intermediates at the AWI. For example, spray ionization mass spectrometric analysis of water microjets exposed to a gaseous mixture of ozone and water vapor combined with a 266 nm laser flash photolysis system (LFP-SIMS) has been used to directly probe organic peroxyl radicals (RO2·) produced by interfacial hydroxyl radicals (OH·) + organic compound reactions. OH· emitted immediately after the laser flash photolysis of carboxylic acid at the gas-liquid interface have been directly detected by time-resolved, laser-induced florescence techniques that can be used to study atmospheric multiphase photoreactions. In this Featured Article, we show some recent experimental advances in the detection of atmospherically important intermediates at the AWI and the associated reaction mechanisms. We also discuss current challenges and future prospects for atmospheric multiphase chemistry.

Strong Polarization of a J=1/2 to 1/2 Transition Arising from Unexpectedly Large Quantum Interference.

We experimentally show that the 1s^{2}2s^{2}2p_{1/2}-1s2s^{2}2p_{1/2}^{2} transition in Pb^{77+} emitted in dielectronic recombination of Pb^{78+} is strongly polarized, although it is an intrinsically unpolarized J=1/2 to 1/2 transition. This unanticipated polarization is shown to be due to quantum interference with radiative recombination. The interference effect has been studied on an asymmetric resonance profile but has never been studied on polarization. In this Letter, we show that the effect on polarization can arise from a different cross term than that responsible for asymmetry, resulting in unexpectedly large polarization even for a nearly symmetric resonance suggesting a small interference.

Structure of crystalline water ice formed through neon matrix sublimation under cryogenic and vacuum conditions.

Ice I has three forms depending on the stacking arrangements of its layers: hexagonal ice Ih, cubic ice Ic, and stacking disordered ice Isd. Below ∼60 K, amorphous water becomes metastable, and the formation of any form of ice I is often implicitly precluded. Using a newly developed low-temperature reflection high-energy electron diffraction (RHEED) technique, we show that crystalline ice with cubic stacking sequences (i.e., ice Ic) formed through Ne sublimation from a solid H2O/Ne (1:1000 ratio) matrix at 13 K. The extent of stacking disorder (disordered cubic and hexagonal stacking sequences) in the ice formed by Ne matrix sublimation is smaller than that in vapor-deposited ice Isd prepared at 143 K and below the limit of detection of low-temperature RHEED. Dependence of the resulting ice structures on the thickness of the H2O/Ne matrix shows that amorphous water first forms in the early stages of Ne sublimation, and the cubic stacking sequence subsequently takes place. As the cubic ice Ic formed here at a much lower temperature (13 K) than previously observed (typically above 78 K), Ne matrix sublimation represents a novel route to the formation of cubic ice Ic under low-temperature and low-pressure conditions.

Impurity contribution to ultraviolet absorption of saturated fatty acids.

Saturated fatty acids are abundant organic compounds in oceans and sea sprays. Their photochemical reactions induced by solar radiation have recently been found as an abiotic source of volatile organic compounds, which serve as precursors of secondary organic aerosols. However, photoabsorption of wavelengths longer than 250 nanometers in liquid saturated fatty acids remains unexplained, despite being first reported in 1931. Here, we demonstrate that the previously reported absorption of wavelengths longer than 250 nanometers by liquid nonanoic acid [CH3(CH2)7COOH)] originates from traces of impurities (0.1% at most) intrinsically contained in nonanoic acid reagents. Absorption cross sections of nonanoic acid newly obtained here indicate that the upper limit of its photolysis rate is three to five orders of magnitude smaller than those for atmospherically relevant carbonyl compounds.

Direct Observation and Quantitative Measurement of OH Radical Desorption During the Ultraviolet Photolysis of Liquid Nonanoic Acid.

Ultraviolet (UV) photolysis of fatty acid surfactants─which cover the surfaces of atmospheric liquid aerosols and are found in the oceans─such as nonanoic acid (NA) has recently been suggested as a source of hydroxyl (OH) radicals in the troposphere. We used laser-induced fluorescence to directly observe OH radicals desorbed from the surface of neat liquid NA as a primary photoproduct following 213 nm irradiation. The upper limit of photoreaction cross section for the OH radical desorption was estimated to be 9.0(4.1) × 10-22 cm2, which is only 1.2 ± 0.8% of the photoreaction cross section established for the photolysis of gas-phase acetic acid monomers. Vibrational sum-frequency generation spectroscopy for liquid NA revealed the hydrogen-bonded, cyclic, dimer structure of the NA molecules at the liquid surface. This dimerization can inhibit the formation of OH radicals and lead the present low photochemical reactivity of liquid NA.

An application of a Si/CdTe Compton camera for the polarization measurement of hard x rays from highly charged heavy ions.

Methods to measure the polarization of x rays from highly charged heavy ions with a significantly higher accuracy than that of the existing technology are needed to explore relativistic and quantum electrodynamics effects, including the Breit interaction. We developed an Electron Beam Ion Trap Compton Camera (EBIT-CC), a new Compton polarimeter with pixelated multi-layer silicon, and cadmium telluride counters. The EBIT-CC detects the three-dimensional position of Compton scattering and photoelectric absorption, and thus, the degree of polarization of incoming x rays can be evaluated. We attached the EBIT-CC on the Tokyo Electron Beam Ion Trap (Tokyo-EBIT) in the University of Electro-Communications. An experiment was performed to evaluate its polarimetric capability through an observation of radiative recombination x rays emitted from highly charged krypton ions, which were generated by the Tokyo-EBIT. The CC of the EBIT-CC was calibrated for the ∼75 keV x rays. We developed event reconstruction and selection procedures and applied them to every registered event. As a result, we successfully obtained the polarization degree with an absolute uncertainty of 0.02. This uncertainty is small enough to probe the difference between the zero-frequency approximation and full-frequency-dependent calculation for the Breit interaction, which is expected for dielectronic recombination x rays of highly charged heavy ions.

Development of a Kingdon ion trap system for trapping externally injected highly charged ions.

We have developed a Kingdon ion trap system for the purpose of the laboratory observation of the x-ray forbidden transitions of highly charged ions (HCIs). Externally injected Ar(q+) (q = 5-7) with kinetic energies of 6q keV were successfully trapped in the ion trap. The energy distribution of trapped ions is discussed in detail on the basis of numerical simulations. The combination of the Kingdon ion trap and the time-of-flight mass spectrometer enabled us to measure precise trapping lifetimes of HCIs. As a performance test of the instrument, we measured trapping lifetimes of Ar(q+) (q = 5-7) under a constant number density of H2 and determined the charge-transfer cross sections of Ar(q+)(q = 5, 6)-H2 collision systems at binary collision energies of a few eV. It was confirmed that the present cross section data are consistent with previous data and the values estimated by some scaling formula.