RuII(α-diimine) or RuIII(α-diimine·–)? Structural, spectroscopic, and theoretical evidence for the stabilization of a prominent metal-to-Ligand charge- transfer excited-state configuration in the ground state

The new compounds [Ru(R-DAB)(acac)2] (R-DAB = 1,4-diorganyl- 1,4-diazabuta-1,3-diene; R = tert-butyl, 4-methoxyphenyl, 2,6-dimethylphenyl; acac– = 2,4-pentanedionate) exhibit intrachelate ring bond lengths 1.297

Optimizing the methods of synthesis for barium hexagonal ferrite: an experimental and theoretical study

M-type barium hexaferrite (BaM) is a hard ferrite, crystallizing in space group P6(3)/mmc possessing a hexagonal magneto-plumbite structure, which consists of alternate hexagonal and spinel blocks. The structure of BaM is thus related to those of garnet and spinel ferrite. However the material has proved difficult to synthesize. By taking into account the presence of the spinel block in barium hexagonal ferrite, highly efficient new synthetic methods were devised with routes significantly different from existing ones. These successful variations in synthetic methods have been derived by taking into account a detailed investigation of the structural features of barium hexagonal ferrite and the least change principle whereby configuration changes are kept to a minimum. Thus considering the relevant mechanisms has helped to improve the synthesis efficiencies for both hydrothermal and co-precipitation methods by choosing conditions that invoke the formation of the cubic block or the less stable Fe3O4. The role played by BaFe2O4 in the synthesis is also discussed. The distribution of iron from reactants or intermediates among different sites was also successfully explained. The proposed mechanisms are based on the principle that the cubic block must be self-assembled to form the final product. Thus, it is believed that these formulated mechanisms should be helpful in designing experiments to obtain a deeper understanding of the synthesis process and to investigate the substitution of magnetic ions with doping ions.

A theoretical investigation of a-Fe2O3–Cr2O3 solid solutions

We have examined the thermodynamic stability of a-Fe2O3–Cr2O3 solid solutions as a function of temperature and composition, using a combination of statistical mechanics with atomistic simulation techniques based on classical interatomic potentials, and the addition of a model magnetic interaction Hamiltonian. Our calculations show that the segregation of the Fe and Cr cations is marginally favourable in energy compared to any other cation distribution, and in fact the energy of any cation configuration of the mixed system is always slightly higher than the combined energies of equivalent amounts of the pure oxides separately. However, the positive enthalpy of mixing is small enough to allow the stabilisation of highly disordered solid solutions at temperatures of B400 K or higher. We have investigated the degree of cation disorder and the effective cell parameters of the mixed oxide as functions of temperature and composition, and we discuss the effect of magnetic interactions and lattice vibrations on the stability of the solid solution.

A review of the theoretical basis for bulk mass flux convective parameterization

Most parameterizations for precipitating convection in use today are bulk schemes, in which an ensemble of cumulus elements with different properties is modelled as a single, representative entraining-detraining plume. We review the underpinning mathematical model for such parameterizations, in particular by comparing it with spectral models in which elements are not combined into the representative plume. The chief merit of a bulk model is that the representative plume can be described by an equation set with the same structure as that which describes each element in a spectral model. The equivalence relies on an ansatz for detrained condensate introduced by Yanai et al. (1973) and on a simplified microphysics. There are also conceptual differences in the closure of bulk and spectral parameterizations. In particular, we show that the convective quasi-equilibrium closure of Arakawa and Schubert (1974) for spectral parameterizations cannot be carried over to a bulk parameterization in a straightforward way. Quasi-equilibrium of the cloud work function assumes a timescale separation between a slow forcing process and a rapid convective response. But, for the natural bulk analogue to the cloud-work function (the dilute CAPE), the relevant forcing is characterised by a different timescale, and so its quasi-equilibrium entails a different physical constraint. Closures of bulk parameterization that use the non-entraining parcel value of CAPE do not suffer from this timescale issue. However, the Yanai et al. (1973) ansatz must be invoked as a necessary ingredient of those closures.

A sensitivity analysis of soil moisture retrieval from the t-w microwave emission model

The potential of the τ-ω model for retrieving the volumetric moisture content of bare and vegetated soil from dual polarisation passive microwave data acquired at single and multiple angles is tested. Measurement error and several additional sources of uncertainty will affect the theoretical retrieval accuracy. These include uncertainty in the soil temperature, the vegetation structure and consequently its microwave singlescattering albedo, and uncertainty in soil microwave emissivity based on its roughness. To test the effects of these uncertainties for simple homogeneous scenes, we attempt to retrieve soil moisture from a number of simulated microwave brightness temperature datasets generated using the τ-ω model. The uncertainties for each influence are estimated and applied to curves generated for typical scenarios, and an inverse model used to retrieve the soil moisture content, vegetation optical depth and soil temperature. The effect of each influence on the theoretical soil moisture retrieval limit is explored, the likelihood of each sensor configuration meeting user requirements is assessed, and the most effective means of improving moisture retrieval indicated.

Review of theoretical models of electromagnetic NDT and their applications

There is an increasing interest in modelling electromagnetic methods of NDT - particularly eddy currents. A collaboration within the International Institute of Welding led to a survey intended to explain to non mathematicians the present scope of modelling. The present review commences with this survey and then points out some of the developments and some of the outstanding problems in transferring modelling into industry.

A simple theoretical model for the intensification of tropical cyclones and polar lows

A simple theoretical model for the intensification of tropical cyclones and polar lows is developed using a minimal set of physical assumptions. These disturbances are assumed to be balanced systems intensifying through the WISHE (Wind-Induced Surface Heat Exchange) intensification mechanism, driven by surface fluxes of heat and moisture into an atmosphere which is neutral to moist convection. The equation set is linearized about a resting basic state and solved as an initial-value problem. A system is predicted to intensify with an exponential perturbation growth rate scaled by the radial gradient of an efficiency parameter which crudely represents the effects of unsaturated processes. The form of this efficiency parameter is assumed to be defined by initial conditions, dependent on the nature of a pre-existing vortex required to precondition the atmosphere to a state in which the vortex can intensify. Evaluation of the simple model using a primitive-equation, nonlinear numerical model provides support for the prediction of exponential perturbation growth. Good agreement is found between the simple and numerical models for the sensitivities of the measured growth rate to various parameters, including surface roughness, the rate of transfer of heat and moisture from the ocean surface, and the scale for the growing vortex.

Acronyms used in theoretical chemistry

An alphabetic list of acronyms used in theoretical chemistry is presented. Some explanatory references have been added to make acronyms better understandable but still more are needed. Critical comments, additional references, etc. are requested.

The molecular structure of hexamethyldigermane determined by gas-phase electron diffraction with theoretical calculations for (CH3)3M-M(CH3)3 Where M = C, Si, and Ge

Gas-phase electron diffraction (GED) data together with results from ab initio molecular orbital calculations (HF and MP2/6-311+G(d,p)) have been used to determine the structure of hexamethyldigermane ((CH3)3Ge-Ge(CH3)3). The equilibrium symmetry is D3d, but the molecule has a very low-frequency, largeamplitude, torsional mode (φCGeGeC) that lowers the thermal average symmetry. The effect of this largeamplitude mode on the interatomic distances was described by a dynamic model which consisted of a set of pseudoconformers spaced at even intervals. The amount of each pseudoconformer was obtained from the ab initio calculations (HF/6-311+G(d,p)). The results for the principal distances (ra) and angles (∠h1) obtained from the combined GED/ab initio (with estimated 1σ uncertainties) are r(Ge-Ge) ) 2.417(2) Å, r(Ge-C) ) 1.956(1) Å, r(C-H) ) 1.097(5) Å, ∠GeGeC ) 110.5(2)°, and ∠GeCH ) 108.8(6)°. Theoretical calculations were performed for the related molecules ((CH3)3Si-Si(CH3)3 and (CH3)3C-C(CH3)3).