On the Meridional Structure of Annular Modes

Using a simple stochastic model, the authors illustrate that the occurrence of a meridional dipole in the first empirical orthogonal function (EOF) of a time-dependent zonal jet is a simple consequence of the north–south excursion of the jet center, and this geometrical fact can be understood without appealing to fluid dynamical principles. From this it follows that one ought not, perhaps, be surprised at the fact that such dipoles, commonly referred to as the Arctic Oscillation (AO) or the Northern Annular Mode (NAM), have robustly been identified in many observational studies and appear to be ubiquitous in atmospheric models across a wide range of complexity.

On the sensitivity of annular mode dynamics to stratospheric radiative timescales

Long decorrelation timescales of the annular mode are observed in the lower stratosphere. This study uses a simple dynamical model, which has been used extensively to study stratosphere-troposphere coupling, to investigate the origin of the long dynamical timescales. Several long runs of the model are completed, with different imposed thermal damping timescales in the stratosphere. The dynamical timescales of the annular mode are found to be largely insensitive to the input thermal damping timescales, producing similar dynamical timescales in all cases below 50hPa. This result suggests that the hypothesis that long timescales in the lower stratosphere are due to long radiative timescales in this region is false.

The influence of bottom topography on the decay of modeled Agulhas rings

The influence of a large meridional submarine ridge on the decay of Agulhas rings is investigated with a 1 and 2-layer setup of the isopycnic primitive-equation ocean model MICOM. In the single-layer case we show that the SSH decay of the ring is primarily governed by bottom friction and secondly by the radiation of Rossby waves. When a topographic ridge is present, the effect of the ridge on SSH decay and loss of tracer from the ring is negligible. However, the barotropic ring cannot pass the ridge due to energy and vorticity constraints. In the case of a two-layer ring the initial SSH decay is governed by a mixed barotropic–baroclinic instability of the ring. Again, radiation of barotropic Rossby waves is present. When the ring passes the topographic ridge, it shows a small but significant stagnation of SSH decay, agreeing with satellite altimetry observations. This is found to be due to a reduction of the growth rate of the m = 2 instability, to conversions of kinetic energy to the upper layer, and to a decrease in Rossby-wave radiation. The energy transfer is related to the fact that coherent structures in the lower layer cannot pass the steep ridge due to energy constraints. Furthermore, the loss of tracer from the ring through filamentation is less than for a ring moving over a flat bottom, related to a decrease in propagation speed of the ring. We conclude that ridges like the Walvis Ridge tend to stabilize a multi-layer ring and reduce its decay.

A reconstructed Siberian High index since A. D. 1599 from Eurasian and North American tree rings

The long-term variability of the Siberian High, the dominant Northern Hemisphere anticyclone during winter, is largely unknown. To investigate how this feature varied prior to the instrumental record, we present a reconstruction of a Dec-Feb Siberian High (SH) index based on Eurasian and North American tree rings. Spanning 1599-1980, it provides information on SH variability over the past four centuries. A decline in the instrumental SH index since the late 1970s, related to Eurasian warming, is the most striking feature over the past four hundred years. It is associated with a highly significant (p < 0.0001) step change in 1989. Significant similar to 3-4 yr spectral peaks in the reconstruction fall within the range of variability of the East Asian winter monsoon (which has also declined recently) and lend further support to proposed relationships between these largescale features of the climate system.

Annular variability and eddy-zonal flow interactions in a simplified atmospheric GCM. Part 1: Characterization of high and low frequency behaviour

Experiments have been performed using a simplified, Newtonian forced, global circulation model to investigate how variability of the tropospheric jet can be characterized by examining the combined fluctuations of the two leading modes of annular variability. Eddy forcing of this variability is analyzed in the phase space of the leading modes using the vertically integrated momentum budget. The nature of the annular variability and eddy forcing depends on the time scale. At low frequencies the zonal flow and baroclinic eddies are in quasi equilibrium and anomalies propagate poleward. The eddies are shown primarily to reinforce the anomalous state and are closely balanced by the linear damping, leaving slow evolution as a residual. At high frequencies the flow is strongly evolving and anomalies are initiated on the poleward side of the tropospheric jet and propagate equatorward. The eddies are shown to drive this evolution strongly: eddy location and amplitude reflect the past baroclinicity, while eddy feedback on the zonal flow may be interpreted in terms of wave breaking associated with baroclinic life cycles in lateral shear.

Spectral functions of half-filled one-dimensional Hubbard rings with varying boundary conditions

We study the effect of varying the boundary condition on: the spectral function of a finite one-dimensional Hubbard chain, which we compute using direct (Lanczos) diagonalization of the Hamiltonian. By direct comparison with the two-body response functions and with the exact solution of the Bethe ansatz equations, we can identify both spinon and holon features in the spectra. At half-filling the spectra have the well-known structure of a low-energy holon band and its shadow-which spans the whole Brillouin zone-and a spinon band present for momenta less than the Fermi momentum. Features related to the twisted boundary condition are cusps in the spinon band. We show that the spectral building principle, adapted to account for both the finite system size and the twisted boundary condition, describes the spectra well in terms of single spinon and holon excitations. We argue that these finite-size effects are a signature of spin-charge separation and that their study should help establish the existence and nature of spin-charge separation in finite-size systems.

On the fast decay of Agulhas rings

The Indian Ocean water that ends up in the Atlantic Ocean detaches from the Agulhas Current retroflection predominantly in the form of Agulhas rings and cyclones. Using numerical Lagrangian float trajectories in a high-resolution numerical ocean model, the fate of coherent structures near the Agulhas Current retroflection is investigated. It is shown that within the Agulhas Current, upstream of the retroflection, the spatial distributions of floats ending in the Atlantic Ocean and floats ending in the Indian Ocean are to a large extent similar. This indicates that Agulhas leakage occurs mostly through the detachment of Agulhas rings. After the floats detach from the Agulhas Current, the ambient water quickly looses its relative vorticity. The Agulhas rings thus seem to decay and loose much of their water in the Cape Basin. A cluster analysis reveals that most water in the Agulhas Current is within clusters of 180 km in diameter. Halfway in the Cape Basin there is an increase in the number of larger clusters with low relative vorticity, which carry the bulk of the Agulhas leakage transport through the Cape Basin. This upward cascade with respect to the length scales of the leakage, in combination with a power law decay of the magnitude of relative vorticity, might be an indication that the decay of Agulhas rings is somewhat comparable to the decay of two-dimensional turbulence.

Solid state annular tautomerism in a molecule containing two imidazole moieties

The X-ray crystal structure of the 1:2 condensate (1) of hydrazine hydrate and 4-methyl-imidazole-5-carboxaldehyde has been determined. The molecule is centrosymmetric crystallising in the space group Fddd with cell dimensions: a = 10.557(14), b = 17.062(22), c = 24.759(27) angstrom. Fourier map shows that the NH hydrogen atom of each imidazole moiety has equal possibility of occupying any of its two ring N atoms. This poses the possibility of finding three tautomers in 1 in the solid state. Consideration of the H-bonding pattern observed in 1 and related B3LYP/6-311+G(2d, p) calculations show that only two tautomers are present in the solid state. The situation is compared with that in the structure of 4(5)-nitro-5(4)-methoxy-imidazole reported previously by Kubicki.

Design of supramolecular beta-sheet forming beta-turns containing aromatic rings and non-coded alpha-aminoisobutyric acid and the formation of flat fibrillar structures through self-assembly

Single crystal X-ray diffraction studies show that the three designed tripeptides Boc-Leu-Aib-m-NA-NO2 (I), Boc-Phe-Aib-m-NA-NO2 (II) and Boc-Pro-Aib-m-ABA-OMe (III) (Aib, -aminoisobutyric acid; m-NA, m-nitroaniline; m-ABA, m-aminobenzoic acid; Boc, t-butyloxycarbonyl) containing aromatic rings in the backbones adopt -turn structures that are self-assembled through intermolecular hydrogen bonds and van der Waals interactions to create layers of -sheets. Solvent-dependent NMR titration and CD studies show that the -turn structures of the peptides also exist in the solution phase. The field emission scanning electron microscopic and transmission electron microscopic images of the peptides in the solid state reveal fibrillar structures of flat morphology that are formed through -sheet mediated self-assembly of the preorganised -turn building blocks.

Synthesis of fused cyclic systems containing medium-sized rings through tandem ROM-RCM of norbornene derivatives embedded in a carbohydrate template

A general approach for the synthesis of fused cyclic systems containing medium-sized rings (7-9) has been developed. The key steps involve a diastereoface-selective Diels-Alder reaction of the dienophiles 4a-d attached to a furanosugar with cyclopentadiene and ring opening (ROM)-ring closing metathesis (RCM) of the resulting norbornene derivatives 10a-d and 11a-d. Diels-Alder reaction of the dienophiles 4a-d with cyclopentadiene in the absence of a catalyst produced 10a-d as the major product arising through addition of the diene to the unhindered Si-face. The most interesting and new aspect of the Diels-Alder reaction of these dienophiles is the accessibility of the Re-face that was blocked by the alkenyl chains under Lewis acid catalysis producing the diastereoisomers 11a-d exclusively. The reversal of facial selectivity from an uncatalyzed reaction to a catalyzed one is unprecedented. The observed stereochemical dichotomy is attributed to rotation of the enone moiety along the or bond linking the sugar moiety during formation of the chelate 13. This makes the Re-face of the enone moiety in 4a-d unhindered. Diels-Alder reaction of the carbocyclic analogue 15 under Lewis acid catalysis produced a 1: 1 mixture of the adducts 16 and 17 confirming the participation of sugar ring oxygen in chelate formation. Finally ROM-RCM of 10a-d and 11a-d with Grubbs' catalyst afforded the cis-syn-cis and cis-anti-cis bicyclo-annulated sugars 21a-d and 23a-d, respectively, containing 7-9 membered rings.

Mononuclear and binuclear ruthenium(II) complexes with 4-(phenyl) thiosemicarbazone of benzaldehyde: a discussion on the relative stabilities of the four-membered and five-membered chelate rings formed by the ligand

Three new ruthenium complexes of the formulae cis-[Ru(PPh3)(2)(BzTscbz)(2)] (1a), [Ru-2(PPh3)(2)(BzTscbz)(4)] (1b) and [Ru(PPh3)(2)(BzTscHbz)(2)](ClO4)(2) (2) [BzTscHbz = 4-(phenyl) thiosemicarbazone of benzaldehyde] have been synthesized and characterized by various physicochemical methods including X-ray structure determinations for 1a and 1b. The relative stabilities of the four-membered versus five-membered chelate rings formed by the deprotonated ligand BzTscbz are discussed on the basis of the experimental results and some semi-empirical as well as DFT calculations. (c) 2005 Elsevier Ltd. All rights reserved.