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.

Novel concepts for a planetary surface exploration rover

Purpose - This paper aims to address some of the needs of present and upcoming rover designs, and introduces novel concepts incorporated in a planetary surface exploration rover design that is currently under development. Design/methodology/approach - The Multitasking Rover (MTR) is a highly re-configurable system that aims to demonstrate functionality that will cover many of the current and future needs such as rough-terrain mobility, modularity and upgradeability. It comprises a surface mobility platform which is highly re-configurable, which offers centre of mass re-allocation and rough terrain stability, and also a set of science/tool packs - individual subsystems encapsulated in packs which the rover picks up, transports and deploys. Findings - Early testing of the suspension system suggests exceptional performance characteristics. Originality/value - Principles employed in the design of the MTR can be used in future rover systems to reduce associated mission costs and at the same time provide multiples the functionality.

Fast northward energy transfer in the Atlantic due to Agulhas rings

The adiabatic transit time of wave energy radiated by an Agulhas ring released in the South Atlantic Ocean to the North Atlantic Ocean is investigated in a two-layer ocean model. Of particular interest is the arrival time of baroclinic energy in the northern part of the Atlantic, because it is related to variations in the meridional overturning circulation. The influence of the Mid-Atlantic Ridge is also studied, because it allows for the conversion from barotropic to baroclinic wave energy and the generation of topographic waves. Barotropic energy from the ring is present in the northern part of the model basin within 10 days. From that time, the barotropic energy keeps rising to attain a maximum 500 days after initiation. This is independent of the presence or absence of a ridge in the model basin. Without a ridge in the model, the travel time of the baroclinic signal is 1300 days. This time is similar to the transit time of the ring from the eastern to the western coast of the model basin. In the presence of the ridge, the baroclinic signal arrives in the northern part of the model basin after approximately 10 days, which is the same time scale as that of the barotropic signal. It is apparent that the ridge can facilitate the energy conversion from barotropic to baroclinic waves and the slow baroclinic adjustment can be bypassed. The meridional overturning circulation, parameterized in two ways as either a purely barotropic or a purely baroclinic phenomenon, also responds after 1300 days. The ring temporarily increases the overturning strength. Th presence of the ridge does not alter the time scales.

An unusual axial–axial combination of alternating cyclic rings in the chair conformations of hexameric water and chlorine-water clusters

An alternating hexameric water (H2O)(6) cluster and a chlorine-water cluster [Cl-2(H2O)(4)](2-) in the chair forms combine axially to each other to form a 1D chain [{Cl-2(H2O)(6)}(2-)](n) in complex [FeL2]Cl center dot(H2O)(3) (L=2-[(2-methylaminoethylimino)-methyl]-phenol)]. The water molecules display extensive H-bonding interactions with monomeric iron-organic units to form a hydrogen-bonded 2D supramolecular assembly.

Constraints on wave drag parameterization schemes for simulating the quasi-biennial oscillation. Part II: combined effects of gravity waves and equatorial planetary waves

This study examines the effect of combining equatorial planetary wave drag and gravity wave drag in a one-dimensional zonal mean model of the quasi-biennial oscillation (QBO). Several different combinations of planetary wave and gravity wave drag schemes are considered in the investigations, with the aim being to assess which aspects of the different schemes affect the nature of the modeled QBO. Results show that it is possible to generate a realistic-looking QBO with various combinations of drag from the two types of waves, but there are some constraints on the wave input spectra and amplitudes. For example, if the phase speeds of the gravity waves in the input spectrum are large relative to those of the equatorial planetary waves, critical level absorption of the equatorial planetary waves may occur. The resulting mean-wind oscillation, in that case, is driven almost exclusively by the gravity wave drag, with only a small contribution from the planetary waves at low levels. With an appropriate choice of wave input parameters, it is possible to obtain a QBO with a realistic period and to which both types of waves contribute. This is the regime in which the terrestrial QBO appears to reside. There may also be constraints on the initial strength of the wind shear, and these are similar to the constraints that apply when gravity wave drag is used without any planetary wave drag. In recent years, it has been observed that, in order to simulate the QBO accurately, general circulation models require parameterized gravity wave drag, in addition to the drag from resolved planetary-scale waves, and that even if the planetary wave amplitudes are incorrect, the gravity wave drag can be adjusted to compensate. This study provides a basis for knowing that such a compensation is possible.

Planetary-wave-induced transport in the stratosphere

In the stratosphere, chemical tracers are drawn systematically from the equator to the pole. This observed Brewer–Dobson circulation is driven by wave drag, which in the stratosphere arises mainly from the breaking and dissipation of planetary-scale Rossby waves. While the overall sense of the circulation follows from fundamental physical principles, a quantitative theoretical understanding of the connection between wave drag and Lagrangian transport is limited to linear, small-amplitude waves. However, planetary waves in the stratosphere generally grow to a large amplitude and break in a strongly nonlinear fashion. This paper addresses the connection between stratospheric wave drag and Lagrangian transport in the presence of strong nonlinearity, using a mechanistic three-dimensional primitive equations model together with offline particle advection. Attention is deliberately focused on a weak forcing regime, such that sudden warmings do not occur and a quasi-steady state is reached, in order to examine this question in the cleanest possible context. Wave drag is directly linked to the transformed Eulerian mean (TEM) circulation, which is often used as a surrogate for mean Lagrangian motion. The results show that the correspondence between the TEM and mean Lagrangian velocities is quantitatively excellent in regions of linear, nonbreaking waves (i.e., outside the surf zone), where streamlines are not closed. Within the surf zone, where streamlines are closed and meridional particle displacements are large, the agreement between the vertical components of the two velocity fields is still remarkably good, especially wherever particle paths are coherent so that diabatic dispersion is minimized. However, in this region the meridional mean Lagrangian velocity bears little relation to the meridional TEM velocity, and reflects more the kinematics of mixing within and across the edges of the surf zone. The results from the mechanistic model are compared with those from the Canadian Middle Atmosphere Model to test the robustness of the conclusions.

Nonlinear symmetric stability of planetary atmospheres

The energy–Casimir method is applied to the problem of symmetric stability in the context of a compressible, hydrostatic planetary atmosphere with a general equation of state. Formal stability criteria for symmetric disturbances to a zonally symmetric baroclinic flow are obtained. In the special case of a perfect gas the results of Stevens (1983) are recovered. Finite-amplitude stability conditions are also obtained that provide an upper bound on a certain positive-definite measure of disturbance amplitude.

A survey for planetary transits in the field of NGC 7789

We present results from 30 nights of observations of the open cluster NGC 7789 with the Wide Field Camera on the Isaac Newton Telescope, La Palma. From ~900 epochs, we obtained light curves and Sloan r'-i' colours for ~33000 stars, with ~2400 stars having better than 1 per cent precision. We expected to detect ~2 transiting hot Jupiter planets if 1 per cent of stars host such a companion and a typical hot Jupiter radius is ~1.2R_J. We find 24 transit candidates, 14 of which we can assign a period. We rule out the transiting planet model for 21 of these candidates using various robust arguments. For two candidates, we are unable to decide on their nature, although it seems most likely that they are eclipsing binaries as well. We have one candidate exhibiting a single eclipse, for which we derive a radius of 1.81+0.09-0.00R_J. Three candidates remain that require follow-up observations in order to determine their nature.

Structure of the planetary boundary layer over southeast England: modeling and measurements

The Weather Research and Forecasting model was applied to analyze variations in the planetary boundary layer (PBL) structure over Southeast England including central and suburban London. The parameterizations and predictive skills of two nonlocal mixing PBL schemes, YSU and ACM2, and two local mixing PBL schemes, MYJ and MYNN2, were evaluated over a variety of stability conditions, with model predictions at a 3 km grid spacing. The PBL height predictions, which are critical for scaling turbulence and diffusion in meteorological and air quality models, show significant intra-scheme variance (> 20%), and the reasons are presented. ACM2 diagnoses the PBL height thermodynamically using the bulk Richardson number method, which leads to a good agreement with the lidar data for both unstable and stable conditions. The modeled vertical profiles in the PBL, such as wind speed, turbulent kinetic energy (TKE), and heat flux, exhibit large spreads across the PBL schemes. The TKE predicted by MYJ were found to be too small and show much less diurnal variation as compared with observations over London. MYNN2 produces better TKE predictions at low levels than MYJ, but its turbulent length scale increases with height in the upper part of the strongly convective PBL, where it should decrease. The local PBL schemes considerably underestimate the entrainment heat fluxes for convective cases. The nonlocal PBL schemes exhibit stronger mixing in the mean wind fields under convective conditions than the local PBL schemes and agree better with large-eddy simulation (LES) studies.

Extracting planetary waves from geomagnetic time series using Empirical Mode Decomposition

Empirical Mode Decomposition is presented as an alternative to traditional analysis methods to decompose geomagnetic time series into spectral components. Important comments on the algorithm and its variations will be given. Using this technique, planetary wave modes of 5-, 10-, and 16-day mean periods can be extracted from magnetic field components of three different stations in Germany. In a second step, the amplitude modulation functions of these wave modes can be shown to contain significant contribution from solar cycle variation through correlation with smoothed sunspot numbers. Additionally, the data indicate connections with geomagnetic jerk occurrences, supported by a second set of data providing reconstructed near-Earth magnetic field for 150 years. Usually attributed to internal dynamo processes within the Earth's outer core, the question of who is impacting whom will be briefly discussed here.

The solsticial pause on Mars: 1. A planetary wave reanalysis

Large-scale planetary waves are diagnosed from an analysis of profiles retrieved from the Thermal Emission Spectrometer aboard the Mars Global Surveyor spacecraft during its scientific mapping phase. The analysis is conducted by assimilating thermal profiles and total dust opacity retrievals into a Mars global circulation model. Transient waves are largest throughout the northern hemisphere autumn, winter and spring period and almost absent during the summer. The southern hemisphere exhibits generally weaker transient wave behaviour. A striking feature of the low-altitude transient waves in the analysis is that they show a broad subsidiary minimum in amplitude centred on the winter solstice, a period when the thermal contrast between the summer hemisphere and the winter pole is strongest and baroclinic wave activity might be expected to be strong. This behaviour, here called the ‘solsticial pause,’ is present in every year of the analysis. This strong pause is under-represented in many independent model experiments, which tend to produce relatively uniform baroclinic wave activity throughout the winter. This paper documents and diagnoses the transient wave solsticial pause found in the analysis; a companion paper investigates the origin of the phenomenon in a series of model experiments.

Tracer Leakage from Modeled Agulhas Rings

In a numerical, isopycnal, ocean model the mixing is investigated with the environment of two idealized Agulhas rings, one that splits, and one that remains coherent. The evolution of a passive tracer , initially contained within the rings, shows that tracer leakage is associated with the for mation of filaments in the early stage of ring evolution. These filaments reach down to the ther mocline. In the deepest layers leakage occurs on a larger scale. Self-advection of the rings is ver y irregular , and it is not possible to compute a Lagrangian boundar y i n order to estimate the transport of leakage from the rings. T o describe the processes that gover n tracer leakage, in a coordinate frame moving with the ring a kinematic separatrix is defined in the streamfunction field for the nondivergent flow . Initially , filaments arise because of the elongation of the ring, which is mainly gover ned by an m 5 2 instability that is collaborating with differential rotation. Because of beta, the symmetr y i s destroyed related to the separatrix associated with a stagnation point in the flow . The filament upstream of the stagnation point grows much faster and is associated with the bulk of tracer leakage. Mixing is enhanced by time dependence of the separatrix. As a result, there are no large differences between the leakage from a coherent ring, where the m 5 2 instability equilibrates, and from a splitting ring, where the m 5 2 instability keeps growing, which confir ms that the amount of leakage is mainly gover ned by the ring’ s initial defor mation combined with unsteady self-advection of the ring and not by the splitting of the ring. The decay of tracer content in the ther mocline shows that in the first months up to 40% of the ring water can be mixed with the environment. In deeper layers the decay of tracer content may reach up to 90%.

Translation, decay and splitting of Agulhas rings in the southeastern Atlantic Ocean

All Agulhas rings that were spawned at the Agulhas retrofiec- tion between 1993 and 1996 (a total of 21 rings) have been monitored using TOPEX/Poseidon satellite altimetry and followed as they moved through the southeastern Atlantic Ocean, decayed, interacted with bottom topography and each other, or dissipated completely. Rings preferentially crossed the Walvis Ridge at its deepest parts. After having crossed this ridge they have lower translational speeds, and their decay rate decreases markedly. Half the decay of long-lived rings takes place in the first 5 months of their lifetimes. In addition to the strong decay of rings in the Cape Basin, about one third of the observed rings do not seem to leave this region at all but totally disintegrate here. The interaction of rings with bottom topography, in particular with the Verna Seamount, is shown frequently to cause splitting of rings. This will enhance mixing of the rings' Indian Ocean water into that of the southern Atlantic. This localized mixing may well provide a considerable source of warm and salty Indian Ocean water into the Atlantic overturning circulation.