4,4 '-Dipyridyl-N,N '-dioxide complexes of metal-thiocyanate/selenocyanate: pi-stacked molecular rods as three-dimensional support for two-dimensional polymeric sheets and intra/interchain S center dot center dot center dot S interaction dependent architecture of the R-2(2)(8) synthon driven assembly of one-dimensional polymeric chains

Three supramolecular complexes of Co(II) using SCN-/SeCN- in combination with 4,4'-dipyridyl-N,N'-dioxide (dpyo), i.e., {[Co(SCN)(2)(dpyo)(2)].(dpyo)}(n) ( 1), {[Co(SCN)(2)(dpyo)(H2O)(2)].(H2O)}(n) ( 2), {[Co(SeCN)(2)(dpyo)(H2O)(2)]center dot(H2O)}(n) ( 3), have been synthesized and characterized by single-crystal X-ray analysis. Complex 1 is a rare example of a dpyo bridged two-dimensional (2D) coordination polymer, and pi-stacked dpyo supramolecular rods are generated by the lattice dpyo, passing through the rhombic grid of stacked layers, resulting in a three-dimensional (3D) superstructure. Complexes 2 and 3 are isomorphous one-dimensional (1D) coordination polymers [-Co-dpyo-Co-] that undergo self-assembly leading to a bilayer architecture derived through an R-2(2)(8) H-bonding synthon between coordinated water and dpyo oxygen. A reinvestigation of coordination polymers [Mn(SCN)(2)(dpyo)( H2O)(MeOH)](n) ( 4) and {[Fe(SCN)(2)(dpyo)(H2O)(2)]center dot(H2O)}(n) ( 5) reported recently by our group [ Manna et al. Indian J. Chem. 2006, 45A, 1813] reveals brick wall topology rather than bilayer architecture is due to the decisive role of S center dot center dot center dot S/Se center dot center dot center dot Se interactions in determining the helical nature in 4 and 5 as compared to zigzag polymeric chains in 2 and 3, although the same R-2(2)(8) synthon is responsible for supramolecular assembly in these complexes.

Structures and negative thermal expansion properties of the one-dimensional cyanides, CuCN, AgCN and AuCN

The behaviour of the lattice parameters of HTCuCN (high-temperature form), AgCN and AuCN have been investigated as a function of temperature over the temperature range 90–490 K. All materials show one-dimensional negative thermal expansion (NTE) along the ––(M––CN)–– chain direction c (ac(HT-CuCN) ¼32.1 10–6 K1, ac(AgCN)¼23.910–6 K1 and ac(AuCN) ¼9.3106 K1 over the temperature range 90–490 K). The origin of this behaviour has been studied using RMC modelling of Bragg and total neutron diffraction data from AgCN and AuCN at 10 and 300 K. These analyses yield details of the local motions within the chains responsible for NTE. The low-temperature form of CuCN, LT-CuCN, has been studied using single-crystal X-ray diffraction. In this form of CuCN, wavelike distortions of the ––(Cu––CN)–– chains occur in the static structure, which are reminiscent of the motions seen in the RMC modelling of AgCN and AuCN, which are responsible for the NTE behaviour.

Redox control of light-induced charge separation in a transition metal cluster: photochemistry of a methyl viologen-substituted [Os-3(CO)10(a-diimine)] cluster

Sub)picosecond transient absorption (TA) and time-resolved infrared (TRIR) spectra of the cluster [OS3(CO)(10-) (AcPy-MV)](2+) (the clication AcPy-MV = Acpy-MV2+ = [2-pyridylacetimine-N-(2-(1'-methyl-4,4'-bipyridine-1,1'-diium-1-yl) ethyl)] (PF6)(2)) (1(2+)) reveal that photoinduced electron transfer to the electron-accepting 4,4'-bipyridine-1,1'diium (MV2+) moiety competes with the fast relaxation of the initially populated sigmapi* excited state of the cluster to the ground state and/or cleavage of an Os-Os bond. The TA spectra of cluster 12 in acetone, obtained by irradiation into its lowest-energy absorption band, show the characteristic absorptions of the one-electron-reduced MV*(+) unit at 400 and 615 nm, in accordance with population of a charge-separated (CS) state in which a cluster-core electron has been transferred to the lowest pi* orbital of the remote MV2+ unit. This assignment is confirmed by picosecond TRIR spectra that show a large shift of the pilot highest-frequency nu(CO) band of 1(2+) by ca. +40 cm(-1), reflecting the photooxidation of the cluster core. The CS state is populated via fast (4.2 x 10(11) s(-1)) and efficient (88%) oxidative quenching of the optically populated sigmapi* excited state and decays biexponentially with lifetimes of 38 and 166 ps (1:2:1 ratio) with a complete regeneration of the parent cluster. About 12% of the cluster molecules in the sigmapi* excited state form long-lived open-core biradicals. In strongly coordinating acetonitrile, however, the cluster core-to-MV2+ electron transfer in cluster 12+ results in the irreversible formation of secondary photoproducts with a photooxidized cluster core. The photochemical behavior of the [Os-3(CO)(10)(alpha-diimine-MV)](2+) (donor-acceptor) dyad can be controlled by an externally applied electronic bias. Electrochemical one-electron reduction of the MV2+ moiety prior to the irradiation reduces its electron-accepting character to such an extent that the photoinduced electron transfer to MV*+ is no longer feasible. Instead, the irradiation of reduced cluster 1(.)+ results in the reversible formation of an open-core zwitterion, the ultimate photoproduct also observed upon irradiation of related nonsubstituted clusters [Os-3(CO)(10)(alpha-diimine)] in strongly coordinating solvents such as acetonitrile.

Bistable systems with stochastic noise: virtues and limits of effective one-dimensional Langevin equations

The understanding of the statistical properties and of the dynamics of multistable systems is gaining more and more importance in a vast variety of scientific fields. This is especially relevant for the investigation of the tipping points of complex systems. Sometimes, in order to understand the time series of given observables exhibiting bimodal distributions, simple one-dimensional Langevin models are fitted to reproduce the observed statistical properties, and used to investing-ate the projected dynamics of the observable. This is of great relevance for studying potential catastrophic changes in the properties of the underlying system or resonant behaviours like those related to stochastic resonance-like mechanisms. In this paper, we propose a framework for encasing this kind of studies, using simple box models of the oceanic circulation and choosing as observable the strength of the thermohaline circulation. We study the statistical properties of the transitions between the two modes of operation of the thermohaline circulation under symmetric boundary forcings and test their agreement with simplified one-dimensional phenomenological theories. We extend our analysis to include stochastic resonance-like amplification processes. We conclude that fitted one-dimensional Langevin models, when closely scrutinised, may result to be more ad-hoc than they seem, lacking robustness and/or well-posedness. They should be treated with care, more as an empiric descriptive tool than as methodology with predictive power.

Direct Computation of Stochastic Flow in Reservoirs with Uncertain Parameters

A direct method is presented for determining the uncertainty in reservoir pressure, flow, and net present value (NPV) using the time-dependent, one phase, two- or three-dimensional equations of flow through a porous medium. The uncertainty in the solution is modelled as a probability distribution function and is computed from given statistical data for input parameters such as permeability. The method generates an expansion for the mean of the pressure about a deterministic solution to the system equations using a perturbation to the mean of the input parameters. Hierarchical equations that define approximations to the mean solution at each point and to the field covariance of the pressure are developed and solved numerically. The procedure is then used to find the statistics of the flow and the risked value of the field, defined by the NPV, for a given development scenario. This method involves only one (albeit complicated) solution of the equations and contrasts with the more usual Monte-Carlo approach where many such solutions are required. The procedure is applied easily to other physical systems modelled by linear or nonlinear partial differential equations with uncertain data.

Eigenvalues of a one-dimensional Dirac operator pencil

We study the spectrum of a one-dimensional Dirac operator pencil, with a coupling constant in front of the potential considered as the spectral parameter. Motivated by recent investigations of graphene waveguides, we focus on the values of the coupling constant for which the kernel of the Dirac operator contains a square integrable function. In physics literature such a function is called a confined zero mode. Several results on the asymptotic distribution of coupling constants giving rise to zero modes are obtained. In particular, we show that this distribution depends in a subtle way on the sign variation and the presence of gaps in the potential. Surprisingly, it also depends on the arithmetic properties of certain quantities determined by the potential. We further observe that variable sign potentials may produce complex eigenvalues of the operator pencil. Some examples and numerical calculations illustrating these phenomena are presented.

A novel ensemble method for retrieving properties of warm cloud in 3-D using ground-based scanning radar and zenith radiances

We present a novel method for retrieving high-resolution, three-dimensional (3-D) nonprecipitating cloud fields in both overcast and broken-cloud situations. The method uses scanning cloud radar and multiwavelength zenith radiances to obtain gridded 3-D liquid water content (LWC) and effective radius (re) and 2-D column mean droplet number concentration (Nd). By using an adaption of the ensemble Kalman filter, radiances are used to constrain the optical properties of the clouds using a forward model that employs full 3-D radiative transfer while also providing full error statistics given the uncertainty in the observations. To evaluate the new method, we first perform retrievals using synthetic measurements from a challenging cumulus cloud field produced by a large-eddy simulation snapshot. Uncertainty due to measurement error in overhead clouds is estimated at 20% in LWC and 6% in re, but the true error can be greater due to uncertainties in the assumed droplet size distribution and radiative transfer. Over the entire domain, LWC and re are retrieved with average error 0.05–0.08 g m-3 and ~2 μm, respectively, depending on the number of radiance channels used. The method is then evaluated using real data from the Atmospheric Radiation Measurement program Mobile Facility at the Azores. Two case studies are considered, one stratocumulus and one cumulus. Where available, the liquid water path retrieved directly above the observation site was found to be in good agreement with independent values obtained from microwave radiometer measurements, with an error of 20 g m-2.

Solvothermal synthesis of one-dimensional chalcogenides containing group 13 elements

The solvothermal synthesis and characterisation of [C6H16N2][GaS2]2 (1), [C6H16N2][Ga2Se3(Se2)] (2), and mixed-metal phases with composition [C6H16N2][Ga2–xInxSe3(Se2)] (0 < x < 2)(3–5), is described. These materials have been characterised by single-crystal and powder X-ray diffraction, thermogravimetric analysis and UV/Vis diffuse reflectance spectroscopy. The materials contain one-dimensional anionic chains. In 1, these chains consist of edge-linked GaS4 tetrahedra, whilst in 2–5, the chains contain perselenide (Se2)2– units and comprise alternating four-membered [M2Se2] and five-membered [M2Se3] rings (where M = Ga, In). Compounds 3–5 represent the first examples of ternary mixed-metal [M2Se3(Se2)]2– chains.

Hydrothermal synthesis of [C6H16N2][In2Se3(Se2)]: a new one-dimensional indium selenide

A new organically templated indium selenide, [C6H16N2][In2Se3(Se2)], has been prepared hydrothermally from the reaction of indium, selenium and trans-1,4-diaminocyclohexane in water at 170 °C. This material was characterised by single-crystal and powder X-ray diffraction, thermogravimetric analysis, UV–vis diffuse reflectance spectroscopy, FT-IR and elemental analysis. The compound crystallises in the monoclinic space group C2/c (a=12.0221(16) Å, b=11.2498(15) Å, c=12.8470(17) Å, β=110.514(6)°). The crystal structure of [C6H16N2][In2Se3(Se2)] contains anionic chains of stoichiometry [In2Se3(Se2)]2−, which are aligned parallel to the [1 0 1] direction, and separated by diprotonated trans-1,4-diaminocyclohexane cations. The [In2Se3(Se2)]2− chains, which consist of alternating four-membered [In2Se2] and five-membered [In2Se3] rings, contain perselenide (Se2)2− units. UV–vis diffuse reflectance spectroscopy indicates that [C6H16N2][In2Se3(Se2)] has a band gap of 2.23(1) eV

Synthesis, characterisation and magnetic properties of a one-dimensional Iron(II) coordination polymer

A new iron(II) coordination polymer, [FeCl2(NC7H9)2(N2C12H12)], has been synthesized under solvothermal conditions and structurally characterized by single-crystal X-ray diffraction. This material crystallizes in the monoclinic space group C2/c, with a = 11.2850(6), b = 13.8925(7), c = 17.0988(9) Å and β = 94.300(3)º (Z = 4). The crystal structure consists of neutral zig-zag chains, in which the iron(II) ions are octahedrally coordinated. The infinite polymer chains are packed into a three-dimensional structure through C–H···Cl interactions. Magnetic susceptibility measurements reveal the existence of weak antiferromagnetic interactions between the iron(II) ions. The effective magnetic moment, μ eff = 5.33 μ B , is consistent with a high-spin iron(II) configuration.

Coupling an aerosol box model with one-dimensional flow: a tool for understanding observations of new particle formation events

Field observations of new particle formation and the subsequent particle growth are typically only possible at a fixed measurement location, and hence do not follow the temporal evolution of an air parcel in a Lagrangian sense. Standard analysis for determining formation and growth rates requires that the time-dependent formation rate and growth rate of the particles are spatially invariant; air parcel advection means that the observed temporal evolution of the particle size distribution at a fixed measurement location may not represent the true evolution if there are spatial variations in the formation and growth rates. Here we present a zero-dimensional aerosol box model coupled with one-dimensional atmospheric flow to describe the impact of advection on the evolution of simulated new particle formation events. Wind speed, particle formation rates and growth rates are input parameters that can vary as a function of time and location, using wind speed to connect location to time. The output simulates measurements at a fixed location; formation and growth rates of the particle mode can then be calculated from the simulated observations at a stationary point for different scenarios and be compared with the ‘true’ input parameters. Hence, we can investigate how spatial variations in the formation and growth rates of new particles would appear in observations of particle number size distributions at a fixed measurement site. We show that the particle size distribution and growth rate at a fixed location is dependent on the formation and growth parameters upwind, even if local conditions do not vary. We also show that different input parameters used may result in very similar simulated measurements. Erroneous interpretation of observations in terms of particle formation and growth rates, and the time span and areal extent of new particle formation, is possible if the spatial effects are not accounted for.

Simulation of monsoon disturbances in the LMD GCM

The monsoon depressions that form over India during the summer are analyzed using simulations from the Laboratoire de Meteorologie Dynamique general circulation model. This type of synoptic system often occurs with a frequency of one to two per month and can produce a strong Indian rainfall. Two kinds of analyses are conducted in this study. The first one is a subjective analysis based on the evolution of the precipitation rate and the pattern of the sea level pressure. The second one is an objective analysis performed using the TRACK program, which identifies and tracks the minima in the sea level pressure anomaly held and computes the statistics for the distribution of systems. The analysis of a 9-yr control run, which simulates strong precipitation rates over the foothills of the Himalayas and over southern India but weak rates over central India, shows that the number of disturbances is coo low and that they almost never occur during August, when break conditions prevail. The generated disturbances more often move north, toward the foothills of the Himalayas. Another analysis is performed to study the effect of the Tibetan Plateau elevation on these disturbances with a 9-yr run carried out with a Tibetan Plateau at 50% of its current height. It is shown that this later integration simulates more frequent monsoon disturbances, which move rather northwestward, in agreement with the current observations. The comparison between the two runs shows that the June-July-August rainfall difference is in large part due to changes in the occurrence of the monsoon disturbances.

Statistical properties of cloud lifecycles in cloud-resolving models

A new technique is described for the analysis of cloud-resolving model simulations, which allows one to investigate the statistics of the lifecycles of cumulus clouds. Clouds are tracked from timestep-to-timestep within the model run. This allows for a very simple method of tracking, but one which is both comprehensive and robust. An approach for handling cloud splits and mergers is described which allows clouds with simple and complicated time histories to be compared within a single framework. This is found to be important for the analysis of an idealized simulation of radiative-convective equilibrium, in which the moist, buoyant, updrafts (i.e., the convective cores) were tracked. Around half of all such cores were subject to splits and mergers during their lifecycles. For cores without any such events, the average lifetime is 30min, but events can lengthen the typical lifetime considerably.

Technical note: A proposed method to determine the extent of degradation of a feed in the rumen from the degradation profile obtained with the in vitro gas production technique using feces as the inoculum

A method is proposed to determine the extent of degradation in the rumen involving a two-stage mathematical modeling process. In the first stage, a statistical model shifts (or maps) the gas accumulation profile obtained using a fecal inoculum to a ruminal gas profile. Then, a kinetic model determines the extent of degradation in the rumen from the shifted profile. The kinetic model is presented as a generalized mathematical function, allowing any one of a number of alternative equation forms to be selected. This method might allow the gas production technique to become an approach for determining extent of degradation in the rumen, decreasing the need for surgically modified animals while still maintaining the link with the animal. Further research is needed before the proposed methodology can be used as a standard method across a range of feeds.