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- ItemThe Hiccup: a dynamical coupling process during the autumn transition in the Northern Hemisphere – similarities and differences to sudden stratospheric warmings(Katlenburg, Lindau : Copernicus, 2015) Matthias, V.; Shepherd, T.G.; Hoffmann, P.; Rapp, M.Sudden stratospheric warmings (SSWs) are the most prominent vertical coupling process in the middle atmosphere, which occur during winter and are caused by the interaction of planetary waves (PWs) with the zonal mean flow. Vertical coupling has also been identified during the equinox transitions, and is similarly associated with PWs. We argue that there is a characteristic aspect of the autumn transition in northern high latitudes, which we call the "hiccup", and which acts like a "mini SSW", i.e. like a small minor warming. We study the average characteristics of the hiccup based on a superimposed epoch analysis using a nudged version of the Canadian Middle Atmosphere Model, representing 30 years of historical data. Hiccups can be identified in about half the years studied. The mesospheric zonal wind results are compared to radar observations over Andenes (69° N, 16° E) for the years 2000–2013. A comparison of the average characteristics of hiccups and SSWs shows both similarities and differences between the two vertical coupling processes.
- ItemEnhanced stratosphere/troposphere coupling during extreme warm stratospheric events with strong polar-night jet oscillation(Basel : MDPI AG, 2018) Peters, D.H.W.; Schneidereit, A.; Karpechko, A.Y.Extreme warm stratospheric events during polar winters from ERA-Interim reanalysis and CMIP5-ESM-LR runs were separated by duration and strength of the polar-night jet oscillation (PJO) using a high statistical confidence level of three standard deviations (strong-PJO events). With a composite analysis, we demonstrate that strong-PJO events show a significantly stronger downward propagating signal in both, northern annular mode (NAM) and zonal mean zonal wind anomaly in the stratosphere in comparison with non-PJO events. The lower stratospheric EP-flux-divergence difference in ERA-Interim was stronger in comparison to long-term CMIP5-ESM-LR runs (by a factor of four). This suggests that stratosphere-troposphere coupling is stronger in ERA-Interim than in CMIP5-ESM-LR. During the 60 days following the central date (CD), the Arctic oscillation signal was more intense during strong-PJO events than during non-PJO events in ERA-Interim data in comparison to CMIP5-ESM-LR runs. During the 15-day phase after CD, strong PJO events had a significant increase in stratospheric ozone, upper tropospheric zonally asymmetric impact, and a regional surface impact in ERA-Interim. Finally, we conclude that the applied high statistical threshold gives a clearer separation of extreme warm stratospheric events into strong-PJO events and non-PJO events including their different downward propagating NAM signal and tropospheric impacts. © 2018 by the authors.
- ItemCoupled and decoupled stratocumulus-topped boundary layers: turbulence properties(Katlenburg-Lindau : European Geosciences Union, 2021) Nowak, Jakub L.; Siebert, Holger; Szodry, Kai-Erik; Malinowski, Szymon P.We compare turbulence properties in coupled and decoupled marine stratocumulus-topped boundary layers (STBLs) using high-resolution in situ measurements performed by the helicopter-borne Airborne Cloud Turbulence Observation System (ACTOS) platform in the region of the eastern North Atlantic. The thermodynamically well-mixed coupled STBL was characterized by a comparable latent heat flux at the surface and in the cloud-top region, and substantially smaller sensible heat flux in the entire depth. Turbulence kinetic energy (TKE) was efficiently generated by buoyancy in the cloud and at the surface, and dissipated with comparable rate across the entire depth. Structure functions and power spectra of velocity fluctuations in the inertial range were reasonably consistent with the predictions of Kolmogorov theory. The turbulence was close to isotropic. In the decoupled STBL, decoupling was most obvious in humidity profiles. Heat fluxes and buoyant TKE production at the surface were similar to the coupled case. Around the transition level, latent heat flux decreased to zero and TKE was consumed by weak stability. In the cloud-top region, heat fluxes almost vanished and buoyancy production was significantly smaller than for the coupled case. The TKE dissipation rate inside the decoupled STBL varied between its sublayers. Structure functions and power spectra in the inertial range deviated from Kolmogorov scaling. This was more pronounced in the cloud and subcloud layer in comparison to the surface mixed layer. The turbulence was more anisotropic than in the coupled STBL, with horizontal fluctuations dominating. The degree of anisotropy was largest in the cloud and subcloud layer of the decoupled STBL. Integral length scales, of the order of 100gm in both cases, indicate turbulent eddies smaller than the depth of the coupled STBL or of the sublayers of the decoupled STBL. We hypothesize that turbulence produced in the cloud or close to the surface is redistributed across the entire coupled STBL but rather only inside the sublayers where it was generated in the case of the decoupled STBL. Scattered cumulus convection, developed below the stratocumulus base, may play a role in transport between those sublayers. © 2021 Jakub L. Nowak et al.
- ItemCarbon Monoxide Coupling Reactions: A New Concept for the Formation of Hexahydroxybenzene(Weinheim : Wiley-VCH, 2020) Rosenthal, UweFor linear and cyclic coupling reactions of CO, among other products, the formation of the hexapotassium salt of hexahydroxybenzene is of particular interesting. The interaction of metallic potassium and CO offers, via the assumed K[OC≡CO]K as the result of several carbon monoxide coupling reactions, the formation of C6(OK)6 among other products. To date, only speculations exist about the reaction pathway for these products, which were first described by Liebig in 1834. A novel concept is suggested here, which consists of the single steps (i) reductive coupling of CO, (ii) formation of dihetero-metallacyclopentynes (cis-2,5-diheterobutatriene as formal ethylenedione O=C=C=O complexes), (iii) formation of its dinuclear 1-metalla-2,5-dioxo-cyclopentyne complexes by external coordination of the triple bond, (iv) insertion of CO into the M−C bond of the formed metallacyclopropene, and (v) the reductive elimination of C6(OK)6. The novel aspect of this concept is the formation of dihetero-metallacyclopentynes (in analogy to the well characterized all-C-metallacyclopentynes), which have not been considered in the mechanism of reductive CO coupling reactions. It is expected that the presence of transition-metal impurities would promote the reaction. © 2020 The Authors. Published by Wiley-VCH GmbH
- ItemChallenges in network science: Applications to infrastructures, climate, social systems and economics(Heidelberg : Springer, 2012) Havlin, S.; Kenett, D.Y.; Ben-Jacob, E.; Bunde, A.; Cohen, R.; Hermann, H.; Kantelhardt, J.W.; Kertész, J.; Kirkpatrick, S.; Kurths, J.; Portugali, J.; Solomon, S.Network theory has become one of the most visible theoretical frameworks that can be applied to the description, analysis, understanding, design and repair of multi-level complex systems. Complex networks occur everywhere, in man-made and human social systems, in organic and inorganic matter, from nano to macro scales, and in natural and anthropogenic structures. New applications are developed at an ever-increasing rate and the promise for future growth is high, since increasingly we interact with one another within these vital and complex environments. Despite all the great successes of this field, crucial aspects of multi-level complex systems have been largely ignored. Important challenges of network science are to take into account many of these missing realistic features such as strong coupling between networks (networks are not isolated), the dynamics of networks (networks are not static), interrelationships between structure, dynamics and function of networks, interdependencies in given networks (and other classes of links, including different signs of interactions), and spatial properties (including geographical aspects) of networks. This aim of this paper is to introduce and discuss the challenges that future network science needs to address, and how different disciplines will be accordingly affected.
- ItemC-F bond activation under transition-metal-free conditions(Beijing : Science China Press, 2021) Ai, Han-Jun; Ma, Xingxing; Song, Qiuling; Wu, Xiao-FengThe unique properties of fluorine-containing organic compounds make fluorine substitution attractive for the development of pharmaceuticals and various specialty materials, which have inspired the evolution of diverse C-F bond activation techniques. Although many advances have been made in functionalizations of activated C-F bonds utilizing transition metal complexes, there are fewer approaches available for nonactivated C-F bonds due to the difficulty in oxidative addition of transition metals to the inert C-F bonds. In this regard, using Lewis acid to abstract the fluoride and light/radical initiator to generate the radical intermediate have emerged as powerful tools for activating those inert C-F bonds. Meanwhile, these transition-metal-free processes are greener, economical, and for the pharmaceutical industry, without heavy metal residues. This review provides an overview of recent C-F bond activations and functionalizations under transition-metal-free conditions. The key mechanisms involved are demonstrated and discussed in detail. Finally, a brief discussion on the existing limitations of this field and our perspective are presented.
- ItemConfidence sets for the optimal approximating model(Berlin : Weierstraß-Institut für Angewandte Analysis und Stochastik, 2008) Rohde, Angelika; Dümbgen, LutzIn the setting of high-dimensional linear models with Gaussian noise, we investigate the possibility of confidence statements connected to model selection. Although there exist numerous procedures for adaptive point estimation, the construction of adaptive confidence regions is severely limited (cf. Li, 1989). The present paper sheds new light on this gap. We develop exact and adaptive confidence sets for the best approximating model in terms of risk. Our construction is based on a multiscale procedure and a particular coupling argument. Utilizing exponential inequalities for noncentral $chi^2$--distributions, we show that the risk and quadratic loss of all models within our confidence region are uniformly bounded by the minimal risk times a factor close to one.
- ItemSharp-optimal adjustment for multiple testing in the multivariate two-sample problem(Berlin : Weierstraß-Institut für Angewandte Analysis und Stochastik, 2008) Rohde, AngelikaBased on two independent samples $X_1, ...,X_m$ and $X_m+1, ...,X_n$ drawn from multivariate distributions with unknown Lebesgue densities p and q respectively, we propose an exact multiple test in order to identify simultaneously regions of significant deviations between p and q. The construction is built from randomized nearestneighbor statistics. It does not require any preliminary information about the multivariate densities such as compact support, strict positivity or smoothness and shape properties. The adjustment for multiple testing is sharp-optimal for typical arrangements of the observation values which appear with probability close to one, and it relies on a new coupling Bernstein type exponential inequality, reflecting the nonsubgaussian tail behavior of the combinatorial process. For power investigation of the proposed method a reparametrized minimax set-up is introduced, reducing the composite hypothesis ''$p = q$'' to a simple one with the multivariate mixed density $(m/n)p + (1 ? m/n)q$ as infinite dimensional nuisance parameter. Within this framework, the test is shown to be spatially and sharply asymptotically adaptive with respect to uniform loss on isotropic Hölder classes.