A new cyano-bridged one-dimensional (GdFeIII)-Fe-III coordination polymer with o-phenanthroline as the blocking ligand: synthesis, structure, and magnetic properties

Synthesis, structural characterization, and magnetic properties of a new cyano-bridged one-dimensional iron (III)-gadolinium (III) compound, trans-[Gd(o-phen)(2)(H2O)(2)(mu-CN)(2)Fe(CN)(4)], - 2no-phen (o-phen = 1,10-phenanthroline), have been described. The compound crystallizes in the triclinic P (1) over bar space group with the following unit cell parameters: a = 10.538(14) angstrom, b = 12.004(14) angstrom, c = 20.61(2) angstrom, alpha = 92.41(1)degrees, beta = 92.76(1)degrees, gamma = 11 2.72(1)degrees, and Z = 2. In this complex, each gadolinium (III) is coordinated to two nitrile nitrogens of the CN groups coming from two different ferricyanides, the mutually trans cyanides of each of which links another different Gd-III to create -NC-Fe(CN)(4)-CN-Gd-NC- type 1-D chain structure. The one-dimensional chains are self-assembled in two-dimensions via weak C-H center dot center dot center dot N hydrogen bonds. Both the variable-temperature (2-300 K, 0.01 T and 0.8 T) and variable-field (0-50 000 Gauss, 2 K) magnetic measurements reveal the existence of very weak interaction in this molecule. The temperature dependence of the susceptibilities has been analyzed using a model for a chain of alternating classic (7/2) and quantum (1/2) spins. (c) 2005 Elsevier B.V. All rights reserved.

Different supramolecular hydrogen bond structures and significant changes in magnetic properties in dinuclear mu(2)-1,1-N-3 copper(II) complexes with very similar tridentate Schiff base blocking ligands

Three new basal-apical, mu(2)-1,1-azide bridged complexes, [CuL1(N-3)](2) (1), [CuL2(N-3)](2) (2) and [CuL3(N-3)]2 (3) with very similar tridentate Schiff base blocking ligands [L-1=N-(3-aminopropyl) salicylaldimine, L-2=7-amino-4-methyl-5-azahept-3-en-2-one and L-3=8-amino-4-methyl-5-azaoct-3-en-2-one) have been synthesised and their molecular structures determined by X-ray crystallography. In complex 1, there is no inter-dimer H-bonding. However, complexes 2 and 3 form two different supramolecular structures in which the dinuclear entities are linked by strong H-bonds giving one-dimensional systems. Variable-temperature (300-2 K) magnetic susceptibility measurements and magnetization measurements at 2 K reveal that complexes 1 and 2 have antiferromagnetic coupling while 3 has ferromagnetic coupling which is also confirmed by EPR spectra at 4-300 K. Magnetostructural correlations have been made taking into consideration both the azido bridging ligands and the existence of intermolecular hydrogen bonds in complexes 2 and 3.

Atmospheric blocking and mean biases in climate models

Models often underestimate blocking in the Atlantic and Pacific basins and this can lead to errors in both weather and climate predictions. Horizontal resolution is often cited as the main culprit for blocking errors due to poorly resolved small-scale variability, the upscale effects of which help to maintain blocks. Although these processes are important for blocking, the authors show that much of the blocking error diagnosed using common methods of analysis and current climate models is directly attributable to the climatological bias of the model. This explains a large proportion of diagnosed blocking error in models used in the recent Intergovernmental Panel for Climate Change report. Furthermore, greatly improved statistics are obtained by diagnosing blocking using climate model data corrected to account for mean model biases. To the extent that mean biases may be corrected in low-resolution models, this suggests that such models may be able to generate greatly improved levels of atmospheric blocking.

Wave-breaking characteristics of midlatitude blocking

In this article, Northern Hemisphere winter midlatitude blocking is analysed through its wave-breaking characteristics. Rossby wave breaking is identified as a key process in blocking occurrence, as it provides the mechanism for the meridional reversal pattern typical of blocking. Two indices are designed to detect the major properties of wave breaking, i.e. the orientation (cyclonic/anticyclonic–direction of breaking or DB index) and the relative contribution of air masses (warm/cold–relative intensity or RI index). The use of the DB index differentiates between the anticyclonic cases over Europe and Asia and the cyclonic events over the oceanic basins. One of the three regions displaying cyclonic type was found over the Atlantic Ocean, the other two being over the Pacific Ocean. The first of these is located over the western side of the Pacific and is dominated by warm air extrusions, whereas the second is placed northward of the exit region of the jet stream, where the meridional θ gradient is much weaker. Two European blocking types have been detected using the RI index, which separates out the cases dominated by warm and cold air masses. The latter cases in particular exhibited a well-structured dipole, with associated strong anomalies in both temperature and precipitation. Copyright © 2011 Royal Meteorological Society

Numerical prediction of atmospheric blocking-A case study

A series of numerical models have been used to investigate the predictability of atmospheric blocking for an episode selected from FGGE Special Observing Period I. Level II-b FGGE data have been used in the experiment. The blocking took place over the North Atlantic region and is a very characteristic example of high winter blocking. It is found that the very high resolution models developed at ECMWF, in a remarkable way manage to predict the blocking event in great detail, even beyond 1 week. Although models with much less resolution manage to predict the blocking phenomenon as such, the actual evolution differs very much from the observed and consequently the practical value is substantially reduced. Wind observations from the geostationary satellites are shown to have a substantial impact on the forecast beyond 5 days, as well as an extension of the integration domain to the whole globe. Quasi-geostrophic baroclinic models and, even more, barotropic models, are totally inadequate to predict blocking except in its initial phase. The prediction experiment illustrates clearly that efforts which have gone into the improvement of numerical prediction models in the last decades have been worth while.

Numerical prediction of atmospheric blocking - A case study

One of the fundamental questions in dynamical meteorology, and one of the basic objectives of GARP, is to determine the predictability of the atmosphere. In the early planning stage and preparation for GARP a number of theoretical and numerical studies were undertaken, indicating that there existed an inherent unpredictability in the atmosphere which even with the most ideal observing system would limit useful weather forecasting to 2-3 weeks.

Review of theories for blocking

A typical feature of the atmospheric circulation at middle and high latitudes is a tendency to fluctuate between two rather extreme circulation patterns. This behaviour of the atmosphere is most common at the Northern Hemisphere during the winter and has been known among the meteorologists for a considerable time (e.g. Garriott (1904)). One of these two states is identified by a predominantly zonal circulation or a so-called high-index circulation, the other state by a meridional or a low-index circulation. The meridional circulation is often broken up in a characteristic atmospheric pattern of cut-off lows and highs. These features usually have a time scale of several days during which they affect the weather in a very dominating way. The transition from the zonal to the meridional or cellular circulation is very characteristic and follows a very typical chain of events.

Wave-breaking characteristics of Northern Hemisphere winter blocking: a two-dimensional approach

This paper generalises and applies recently developed blocking diagnostics in a two- dimensional latitude-longitude context, which takes into consideration both mid- and high-latitude blocking. These diagnostics identify characteristics of the associated wave-breaking as seen in the potential temperature (θ) on the dynamical tropopause, in particular the cyclonic or anticyclonic Direction of wave-Breaking (DB index), and the Relative Intensity (RI index) of the air masses that contribute to blocking formation. The methodology is extended to a 2-D domain and a cluster technique is deployed to classify mid- and high-latitude blocking according to the wave-breaking characteristics. Mid-latitude blocking is observed over Europe and Asia, where the meridional gradient of θ is generally weak, whereas high-latitude blocking is mainly present over the oceans, to the north of the jet-stream, where the meridional gradient of θ is much stronger. They occur respectively on the equatorward and poleward flank of the jet- stream, where the horizontal shear ∂u/∂y is positive in the first case and negative in the second case. A regional analysis is also conducted. It is found that cold-anticyclonic and cyclonic blocking divert the storm-track respectively to the south and to the north over the East Atlantic and western Europe. Furthermore, warm-cyclonic blocking over the Pacific and cold-anticyclonic blocking over Europe are identified as the most persistent types and are associated with large amplitude anomalies in temperature and precipitation. Finally, the high-latitude, cyclonic events seem to correlate well with low- frequency modes of variability over the Pacific and Atlantic Ocean.

Winter and Summer Northern Hemisphere blocking in CMIP5 models

The frequencies of atmospheric blocking in both winter and summer and the changes in them from the 20th to the 21st centuries as simulated in twelve CMIP5 models is analysed. The RCP 8.5 high emission scenario runs are used to represent the 21st century. The analysis is based on the wave-breaking methodology of Pelly and Hoskins (2003a). It differs from the Tibaldi and Molteni (1990) index in viewing equatorward cut-off lows and poleward blocking highs in equal manner as indicating a disruption to the westerlies. 1-dimensional and 2-dimensional diagnostics are applied to identify blocking of the mid-latitude storm-track and also at higher latitudes. Winter blocking frequency is found to be generally underestimated. The models give a decrease in the European blocking maximum in the 21st century, consistent with the results in other studies. There is a mean 21st century winter poleward shift of high- latitude blocking, but little agreement between the models on the details. In summer, Eurasian blocking is also underestimated in the models, whereas it is now too large over the high-latitude ocean basins. A decrease in European blocking frequency in the 21st century model runs is again found. However in summer there is a clear eastward shift of blocking over Eastern Europe and Western Russia, in a region close to the blocking that dominated the Russian summer of 2010. While summer blocking decreases in general, the poleward shift of the storm track into the region of frequent high latitude blocking may mean that the incidence of storms being obstructed by blocks may actually increase.

Atmospheric blocking in a high resolution climate model: influences of mean state, orography and eddy forcing

An underestimate of atmospheric blocking occurrence is a well-known limitation of many climate models. This article presents an analysis of Northern Hemisphere winter blocking in an atmospheric model with increased horizontal resolution. European blocking frequency increases with model resolution, and this results from an improvement in the atmospheric patterns of variability as well as a simple improvement in the mean state. There is some evidence that the transient eddy momentum forcing of European blocks is increased at high resolution, which could account for this. However, it is also shown that the increase in resolution of the orography is needed to realise the improvement in blocking, consistent with the increase in height of the Rocky Mountains acting to increase the tilt of the Atlantic jet stream and giving higher mean geopotential heights over northern Europe. Blocking frequencies in the Pacific sector are also increased with atmospheric resolution, but in this case the improvement in orography actually leads to a decrease in blocking

Northern Hemisphere atmospheric blocking as simulated by 15 atmospheric general circulation models in the period 1979-1988

As a part of the Atmospheric Model Intercomparison Project (AMIP), the behaviour of 15 general circulation models has been analysed in order to diagnose and compare the ability of the different models in simulating Northern Hemisphere midlatitude atmospheric blocking. In accordance with the established AMIP procedure, the 10-year model integrations were performed using prescribed, time-evolving monthly mean observed SSTs spanning the period January 1979–December 1988. Atmospheric observational data (ECMWF analyses) over the same period have been also used to verify the models results. The models involved in this comparison represent a wide spectrum of model complexity, with different horizontal and vertical resolution, numerical techniques and physical parametrizations, and exhibit large differences in blocking behaviour. Nevertheless, a few common features can be found, such as the general tendency to underestimate both blocking frequency and the average duration of blocks. The problem of the possible relationship between model blocking and model systematic errors has also been assessed, although without resorting to ad-hoc numerical experimentation it is impossible to relate with certainty particular model deficiencies in representing blocking to precise parts of the model formulation.