Kinetic regimes and limiting cases of gas uptake and heterogeneous reactions in atmospheric aerosols and clouds: a general classification scheme

Heterogeneous reactions are important to atmospheric chemistry and are therefore an area of intense research. In multiphase systems such as aerosols and clouds, chemical reactions are usually strongly coupled to a complex sequence of mass transport processes and results are often not easy to interpret. Here we present a systematic classification scheme for gas uptake by aerosol or cloud particles which distinguishes two major regimes: a reaction-diffusion regime and a mass transfer regime. Each of these regimes includes four distinct limiting cases, characterised by a dominant reaction location (surface or bulk) and a single rate-limiting process: chemical reaction, bulk diffusion, gas-phase diffusion or mass accommodation. The conceptual framework enables efficient comparison of different studies and reaction systems, going beyond the scope of previous classification schemes by explicitly resolving interfacial transport processes and surface reactions limited by mass transfer from the gas phase. The use of kinetic multi-layer models instead of resistor model approaches increases the flexibility and enables a broader treatment of the subject, including cases which do not fit into the strict limiting cases typical of most resistor model formulations. The relative importance of different kinetic parameters such as diffusion, reaction rate and accommodation coefficients in this system is evaluated by a quantitative global sensitivity analysis. We outline the characteristic features of each limiting case and discuss the potential relevance of different regimes and limiting cases for various reaction systems. In particular, the classification scheme is applied to three different datasets for the benchmark system of oleic acid reacting with ozone in order to demonstrate utility and highlight potential issues. In light of these results, future directions of research needed to elucidate the multiphase chemical kinetics in this and other reaction systems are discussed

Competition between water uptake and ice nucleation by glassy organic aerosol particles

Berkemeier T, Shiraiwa M, Poeschl U, Koop T. Competition between water uptake and ice nucleation by glassy organic aerosol particles. Atmospheric Chemistry and Physics. 2014;14(22):12513-12531.Organic aerosol particles play a key role in climate by serving as nuclei for clouds and precipitation. Their sources and composition are highly variable, and their phase state ranges from liquid to solid under atmospheric conditions, affecting the pathway of activation to cloud droplets and ice crystals. Due to slow diffusion of water in the particle phase, organic particles may deviate in phase and morphology from their thermodynamic equilibrium state, hampering the prediction of their influence on cloud formation. We overcome this problem by combining a novel semi-empirical method for estimation of water diffusivity with a kinetic flux model that explicitly treats water diffusion. We estimate timescales for particle deliquescence as well as various ice nucleation pathways for a wide variety of organic substances, including secondary organic aerosol (SOA) from the oxidation of isoprene, alpha-pinene, naphthalene, and dodecane. The simulations show that, in typical atmospheric updrafts, glassy states and solid/liquid core-shell morphologies can persist for long enough that heterogeneous ice nucleation in the deposition and immersion mode can dominate over homogeneous ice nucleation. Such competition depends strongly on ambient temperature and relative humidity as well as humidification rate and particle size. Due to differences in glass transition temperature, hygroscopicity and atomic O/C ratio of the different SOA, naphthalene SOA particles have the highest potential to act as heterogeneous ice nuclei. Our findings demonstrate that kinetic limitations of water diffusion into organic aerosol particles are likely to be encountered under atmospheric conditions and can strongly affect ice nucleation pathways. For the incorporation of ice nucleation by organic aerosol particles into atmospheric models, our results demonstrate a demand for model formalisms that account for the effects of molecular diffusion and not only describe ice nucleation onsets as a function of temperature and relative humidity but also include updraft velocity, particle size and composition

Design of beam optics for the Future Circular Collider e+e- -collider rings

A beam optics scheme has been designed for the Future Circular Collider-e+e- (FCC-ee). The main characteristics of the design are: beam energy 45 to 175 GeV, 100 km circumference with two interaction points (IPs) per ring, horizontal crossing angle of 30 mrad at the IP and the crab-waist scheme [1] with local chromaticity correction. The crab-waist scheme is implemented within the local chromaticity correction system without additional sextupoles, by reducing the strength of one of the two sextupoles for vertical chromatic correction at each side of the IP. So-called "tapering" of the magnets is applied, which scales all fields of the magnets according to the local beam energy to compensate for the effect of synchrotron radiation (SR) loss along the ring. An asymmetric layout near the interaction region reduces the critical energy of SR photons on the incoming side of the IP to values below 100 keV, while matching the geometry to the beam line of the FCC proton collider (FCC-hh) [2] as closely as possible. Sufficient transverse/longitudinal dynamic aperture (DA) has been obtained, including major dynamical effects, to assure an adequate beam lifetime in the presence of beamstrahlung and top-up injection. In particular, a momentum acceptance larger than +/-2% has been obtained, which is better than the momentum acceptance of typical collider rings by about a factor of 2. The effects of the detector solenoids including their compensation elements are taken into account as well as synchrotron radiation in all magnets. The optics presented in this paper is a step toward a full conceptual design for the collider. A number of issues have been identified for further study

M\"ossbauer, nuclear inelastic scattering and density functional studies on the second metastable state of Na2[Fe(CN)5NO]⋅\cdot2H2O

The structure of the light-induced metastable state SII of Na2[Fe(CN)5NO]$\cdot$2H2O 14 was investigated by transmission M\"ossbauer spectroscopy (TMS) in the temperature range 15 between 85 and 135 K, nuclear inelastic scattering (NIS) at 98 K using synchrotron 16 radiation and density functional theory (DFT) calculations. The DFT and TMS results 17 strongly support the view that the NO group in SII takes a side-on molecular orientation 18 and, further, is dynamically displaced from one eclipsed, via a staggered, to a second 19 eclipsed orientation. The population conditions for generating SII are optimal for 20 measurements by TMS, yet they are modest for accumulating NIS spectra. Optimization 21 of population conditions for NIS measurements is discussed and new NIS experiments on 22 SII are proposed

The {\eta}'-carbon potential at low meson momenta

The production of $\eta^\prime$ mesons in coincidence with forward-going protons has been studied in photon-induced reactions on $^{12}$C and on a liquid hydrogen (LH$_2$) target for incoming photon energies of 1.3-2.6 GeV at the electron accelerator ELSA. The $\eta^\prime$ mesons have been identified via the $\eta^\prime\rightarrow \pi^0 \pi^0\eta \rightarrow 6 \gamma$ decay registered with the CBELSA/TAPS detector system. Coincident protons have been identified in the MiniTAPS BaF$_2$ array at polar angles of $2^{\circ} \le \theta _{p} \le 11^{\circ}$. Under these kinematic constraints the $\eta^\prime$ mesons are produced with relatively low kinetic energy ($\approx$ 150 MeV) since the coincident protons take over most of the momentum of the incident-photon beam. For the C-target this allows the determination of the real part of the $\eta^\prime$-carbon potential at low meson momenta by comparing with collision model calculations of the $\eta^\prime$ kinetic energy distribution and excitation function. Fitting the latter data for $\eta^\prime$ mesons going backwards in the center-of-mass system yields a potential depth of V = $-$(44 $\pm$ 16(stat)$\pm$15(syst)) MeV, consistent with earlier determinations of the potential depth in inclusive measurements for average $\eta^\prime$ momenta of $\approx$ 1.1 GeV/$c$. Within the experimental uncertainties, there is no indication of a momentum dependence of the $\eta^\prime$-carbon potential. The LH$_2$ data, taken as a reference to check the data analysis and the model calculations, provide differential and integral cross sections in good agreement with previous results for $\eta^\prime$ photoproduction off the free proton.Comment: 9 pages, 13 figures. arXiv admin note: text overlap with arXiv:1608.0607

First measurement of the helicity asymmetry for γp→pπ0\gamma p\rightarrow p\pi^0 in the resonance region

The first measurement of the helicity dependence of the photoproduction cross section of single neutral pions off protons is reported for photon energies from 600 to 2300\,MeV, covering nearly the full solid angle. The data are compared to predictions from the SAID, MAID, and BnGa partial wave analyses. Strikingly large differences between data and predictions are observed which are traced to differences in the helicity amplitudes of well known and established resonances. Precise values for the helicity amplitudes of several resonances are reported

The polarization observables T, P, and H and their impact on γp→pπ0\gamma p \to p\pi^0 multipoles

Data on the polarization observables T, P, and H for the reaction $\gamma p\to p\pi^0$ are reported. Compared to earlier data from other experiments, our data are more precise and extend the covered range in energy and angle substantially. The results were extracted from azimuthal asymmetries measured using a transversely polarized target and linearly polarized photons. The data were taken at the Bonn electron stretcher accelerator ELSA with the CBELSA/TAPS detector. Within the Bonn-Gatchina partial wave analysis, the new polarization data lead to a significant narrowing of the error band for the multipoles for neutral-pion photoproduction