The effect of the molecular weight on the electro-optic properties of methacrylate-based side-chain liquid crystal polymers

A series of methacrylate-based side-chain liquid crystal polymers has been prepared with a range of molecular weights. For the high molecular weight polymers a smectic phase is observed with a very narrow nematic range; however, for low molecular weight polymers only the nematic phase is observed. A marked reduction in the glass transition temperature, TSN and TNI is observed with a reduction in the molecular weight. The orientational order parameters for these polymers in the liquid crystal phase have been determined using infra-red dichroism. It is found that the higher the molecular weight of the polymer, the greater is the threshold voltage of the electro-optic response and the lower the order parameter. The increase in the threshold voltage with increasing molecular weight may be related to the intrinsic curvature elasticity and hence to the coupling between the mesogenic units and the polymer backbone.

The effect of annealing on the local structure of glassy polycarbonate

Annealing of polycarbonate glasses at temperatures belowTg leads to an increase in yield stress and a drop in the impact strength. Although such behaviour may be related to the corresponding reduction in free volume upon annealing, variations in the wide-angle X-ray scattering curves indicate some modification to the local structure. The area of an intrachain peak at s ∼ 0.7 Å−1 is monitored with respect to annealing temperature and time. It is proposed that the variations may be described by an increasing level of interlocking or (nesting) between neighbouring chain segments, a process which is a natural consequence of the molecular shape of polycarbonate.

The effect of nonlinearity on the variational assimilation of satellite observations using a simple column model

Cloud imagery is not currently used in numerical weather prediction (NWP) to extract the type of dynamical information that experienced forecasters have extracted subjectively for many years. For example, rapidly developing mid-latitude cyclones have characteristic signatures in the cloud imagery that are most fully appreciated from a sequence of images rather than from a single image. The Met Office is currently developing a technique to extract dynamical development information from satellite imagery using their full incremental 4D-Var (four-dimensional variational data assimilation) system. We investigate a simplified form of this technique in a fully nonlinear framework. We convert information on the vertical wind field, w(z), and profiles of temperature, T(z, t), and total water content, qt (z, t), as functions of height, z, and time, t, to a single brightness temperature by defining a 2D (vertical and time) variational assimilation testbed. The profiles of w, T and qt are updated using a simple vertical advection scheme. We define a basic cloud scheme to obtain the fractional cloud amount and, when combined with the temperature field, we convert this information into a brightness temperature, having developed a simple radiative transfer scheme. With the exception of some matrix inversion routines, all our code is developed from scratch. Throughout the development process we test all aspects of our 2D assimilation system, and then run identical twin experiments to try and recover information on the vertical velocity, from a sequence of observations of brightness temperature. This thesis contains a comprehensive description of our nonlinear models and assimilation system, and the first experimental results.

Preventing carbon contamination of optical devices for X-rays: the effect of oxygen on photon-induced dissociation of CO on platinum

Platinum is one of the most common coatings used to optimize mirror reflectivity in soft X-ray beamlines. Normal operation results in optics contamination by carbon-based molecules present in the residual vacuum of the beamlines. The reflectivity reduction induced by a carbon layer at the mirror surface is a major problem in synchrotron radiation sources. A time-dependent photoelectron spectroscopy study of the chemical reactions which take place at the Pt(111) surface under operating conditions is presented. It is shown that the carbon contamination layer growth can be stopped and reversed by low partial pressures of oxygen for optics operated in intense photon beams at liquidnitrogen temperature. For mirrors operated at room temperature the carbon contamination observed for equivalent partial pressures of CO is reduced and the effects of oxygen are observed on a long time scale.

A unifying framework for metrics for aggregating the climate effect of different emissions

Multi-gas approaches to climate change policies require a metric establishing ‘equivalences’ among emissions of various species. Climate scientists and economists have proposed four kinds of such metrics and debated their relative merits. We present a unifying framework that clarifies the relationships among them. We show, as have previous authors, that the global warming potential (GWP), used in international law to compare emissions of greenhouse gases, is a special case of the global damage potential (GDP), assuming (1) a finite time horizon, (2) a zero discount rate, (3) constant atmospheric concentrations, and (4) impacts that are proportional to radiative forcing. Both the GWP and GDP follow naturally from a cost–benefit framing of the climate change issue. We show that the global temperature change potential (GTP) is a special case of the global cost potential (GCP), assuming a (slight) fall in the global temperature after the target is reached. We show how the four metrics should be generalized if there are intertemporal spillovers in abatement costs, distinguishing between private (e.g., capital stock turnover) and public (e.g., induced technological change) spillovers. Both the GTP and GCP follow naturally from a cost-effectiveness framing of the climate change issue. We also argue that if (1) damages are zero below a threshold and (2) infinitely large above a threshold, then cost-effectiveness analysis and cost–benefit analysis lead to identical results. Therefore, the GCP is a special case of the GDP. The UN Framework Convention on Climate Change uses the GWP, a simplified cost–benefit concept. The UNFCCC is framed around the ultimate goal of stabilizing greenhouse gas concentrations. Once a stabilization target has been agreed under the convention, implementation is clearly a cost-effectiveness problem. It would therefore be more consistent to use the GCP or its simplification, the GTP.

Latitudinal variation of the effect of aviation NOx emissions on atmospheric ozone and methane and related climate metrics

We evaluate the response to regional and latitudinal changes in aircraft NOx emissions using several climate metrics (radiative forcing (RF), Global Warming Potential (GWP), Global Temperature change Potential (GTP)). Global chemistry transport model integrations were performed with sustained perturbations in regional aircraft and aircraft-like NOx emissions. The RF due to the resulting ozone and methane changes is then calculated. We investigate the impact of emission changes for specific geographical regions (approximating to USA, Europe, India and China) and cruise altitude emission changes in discrete latitude bands covering both hemispheres. We find that lower latitude emission changes (per Tg N) cause ozone and methane RFs that are about a factor of 6 larger than those from higher latitude emission changes. The net RF is positive for all experiments. The meridional extent of the RF is larger for low latitude emissions. GWPs for all emission changes are positive, with tropical emissions having the largest values; the sign of the GTP depends on the choice of time horizon.

Effect of anionic co-ligands on structure and magnetic coupling of bis(μ-phenoxo-bridged dinuclear copper(II) complexes

Two phenoxo bridged dinuclear Cu(II) complexes, [Cu2L2(NO2)(2)] (1) and [Cu2L2(NO3)(2)] (2) have been synthesized using the tridentate reduced Schiff-base ligand 2-[(2-dimethylamino-ethylamino)-methyl]-phenol (HL). The complexes have been characterized by X-ray structural analyses and variable-temperature magnetic susceptibility measurements. The structures of the two compounds are very similar having the same tridentate chelating ligand (L) and mono-dentate anionic ligand nitrite for 1 and nitrate for 2. In both complexes Cu(II) is penta-coordinated but the square pyramidal geometry of the copper ions is severely distorted (Addison parameter (tau) = 0.33) in 1 while the distortion is quite small (average tau = 0.11) in 2. These differences have marked effect on the magnetic properties of two compounds. Although both are antiferromagnetically coupled, the coupling constants (J = -140.8 and -614.7 cm (1) for 1 and 2, respectively) show that the coupling is much stronger in 2.

The effect of regional changes in anthropogenic aerosols on rainfall of the East Asian summer monsoon

The response of East Asian Summer Monsoon (EASM) precipitation to long term changes in regional anthropogenic aerosols (sulphate and black carbon) is explored in an atmospheric general circulation model, the atmospheric component of the UK High-Resolution Global Environment Model v1.2 (HiGAM). Separately, sulphur dioxide (SO2) and black carbon (BC) emissions in 1950 and 2000 over East Asia are used to drive model simulations, while emissions are kept constant at year 2000 level outside this region. The response of the EASM is examined by comparing simulations driven by aerosol emissions representative of 1950 and 2000. The aerosol radiative effects are also determined using an off-line radiative transfer model. During June, July and August, the EASM was not significantly changed as either SO2 or BC emissions increased from 1950 to 2000 levels. However, in September, precipitation is significantly decreased by 26.4% for sulphate aerosol and 14.6% for black carbon when emissions are at the 2000 level. Over 80% of the decrease is attributed to changes in convective precipitation. The cooler land surface temperature over China in September (0.8 °C for sulphate and 0.5 °C for black carbon) due to increased aerosols reduces the surface thermal contrast that supports the EASM circulation. However, mechanisms causing the surface temperature decrease in September are different between sulphate and BC experiments. In the sulphate experiment, the sulphate direct and the 1st indirect radiative effects contribute to the surface cooling. In the BC experiment, the BC direct effect is the main driver of the surface cooling, however, a decrease in low cloud cover due to the increased heating by BC absorption partially counteracts the direct effect. This results in a weaker land surface temperature response to BC changes than to sulphate changes. The resulting precipitation response is also weaker, and the responses of the monsoon circulation are different for sulphate and black carbon experiments. This study demonstrates a mechanism that links regional aerosol emission changes to the precipitation changes of the EASM, and it could be applied to help understand the future changes in EASM precipitation in CMIP5 simulations.

Some numerical experiments on the effect of the variation of static stability in two-layer quasi-geostrophic models

A method to solve a quasi-geostrophic two-layer model including the variation of static stability is presented. The divergent part of the wind is incorporated by means of an iterative procedure. The procedure is rather fast and the time of computation is only 60–70% longer than for the usual two-layer model. The method of solution is justified by the conservation of the difference between the gross static stability and the kinetic energy. To eliminate the side-boundary conditions the experiments have been performed on a zonal channel model. The investigation falls mainly into three parts: The first part (section 5) contains a discussion of the significance of some physically inconsistent approximations. It is shown that physical inconsistencies are rather serious and for these inconsistent models which were studied the total kinetic energy increased faster than the gross static stability. In the next part (section 6) we are studying the effect of a Jacobian difference operator which conserves the total kinetic energy. The use of this operator in two-layer models will give a slight improvement but probably does not have any practical use in short periodic forecasts. It is also shown that the energy-conservative operator will change the wave-speed in an erroneous way if the wave-number or the grid-length is large in the meridional direction. In the final part (section 7) we investigate the behaviour of baroclinic waves for some different initial states and for two energy-consistent models, one with constant and one with variable static stability. According to the linear theory the waves adjust rather rapidly in such a way that the temperature wave will lag behind the pressure wave independent of the initial configuration. Thus, both models give rise to a baroclinic development even if the initial state is quasi-barotropic. The effect of the variation of static stability is very small, qualitative differences in the development are only observed during the first 12 hours. For an amplifying wave we will get a stabilization over the troughs and an instabilization over the ridges.

The effect of non-uniform radiative damping on the zonal-mean dynamics of the extratropical middle atmosphere

The effect of spatial and temporal variations in the radiative damping rate on the response to an imposed forcing or diabatic heating is examined in a zonal-mean model of the middle atmosphere. Attention is restricted to the extratropics, where a linear approach is viable. It is found that regions with weak radiative damping rates are more sensitive in terms of temperature to the remote influence of the diabatic circulation. The delay in the response in such regions can mean that ‘downward’ control is not achieved on seasonal time-scales. A seasonal variation in the radiative damping rate modulates the evolution of the response and leaves a transient-like signature in the annual mean temperature field. Several idealized examples are considered, motivated by topical questions. It is found that wave drag outside the polar vortex can significantly affect the temperatures in its interior, so that high-latitude, high-altitude gravity-wave drag is not the only mechanism for warming the southern hemisphere polar vortex. Diabatic mass transport through the 100 hPa surface is found to lag the seasonal evolution of the wave drag that drives the transport, and thus cannot be considered to be in the downward control regime. On the other hand, the seasonal variation of the radiative damping rate is found to make only a weak contribution to the annual mean temperature increase that has been observed above the ozone hole. Copyright © 2002 Royal Meteorological Society.

Effect of provenance, plant part and processing on extract profiles from cultivated European Rhodiola rosea L. for medicinal use.

The demand for plant material of Rhodiola rosea L. (Crassulaceae) for medicinal use has increased recently, amid concerns about its quality and sustainability. We have analysed the content of phenylpropanoids (total rosavins) and salidroside in liquid extracts from 3-year old cultivated plants of European origin, and mapped the influence of plant part (rhizome versus root), genotype, drying, cutting, and extraction solvent to chemical composition. Rhizomes contained 1.5-4 times more salidroside (0.3-0.4% dry wt) and total rosavins (1.2-3.0%) than roots. The qualitative decisive phenylpropanoid content in the extracts was most influenced by plant part, solvent, and genotype, while drying temperature and cutting conditions were of less importance. We have shown that R. rosea from different boreal European provenances can be grown under temperate conditions and identified factors to obtain consistent high quality extracts provided that authentic germplasm is used and distinguished between rhizome, roots and their mixtures.

The effect of climate policy on the impacts of climate change on river flows in the UK

This paper compares the effects of two indicative climate mitigation policies on river flows in six catchments in the UK with two scenarios representing un-mitigated emissions. It considers the consequences of uncertainty in both the pattern of catchment climate change as represented by different climate models and hydrological model parameterisation on the effects of mitigation policy. Mitigation policy has little effect on estimated flow magnitudes in 2030. By 2050 a mitigation policy which achieves a 2oC temperature rise target reduces impacts on low flows by 20-25% compared to a business-as-usual emissions scenario which increases temperatures by 4oC by the end of the 21st century, but this is small compared to the range in impacts between different climate model scenarios. However, the analysis also demonstrates that an early peak in emissions would reduce impacts by 40-60% by 2080 (compared with the 4oC pathway), easing the adaptation challenge over the long term, and can delay by several decades the impacts that would be experienced from around 2050 in the absence of policy. The estimated proportion of impacts avoided varies between climate model patterns and, to a lesser extent, hydrological model parameterisations, due to variations in the projected shape of the relationship between climate forcing and hydrological response.

The effect of increased convective entrainment on Asian monsoon biases in the MetUM General Circulation Model

We demonstrate that summer precipitation biases in the South Asian monsoon domain are sensitive to increasing the convective parametrisation’s entrainment and detrainment rates in the Met Office Unified Model. We explore this sensitivity to improve our understanding of the biases and inform efforts to improve convective parametrisation. We perform novel targeted experiments in which we increase the entrainment and detrainment rates in regions of especially large precipitation bias. We use these experiments to determine whether the sensitivity at a given location is a consequence of the local change to convection or is a remote response to the change elsewhere. We find that a local change leads to different mean-state responses in comparable regions. When the entrainment and detrainment rates are increased globally, feedbacks between regions usually strengthen the local responses. We choose two regions of tropical ascent that show different mean-state responses, the western equatorial Indian Ocean and western north Pacific, and analyse them as case studies to determine the mechanisms leading to the different responses. Our results indicate that several aspects of a region’s mean-state, including moisture content, sea surface temperature and circulation, play a role in local feedbacks that determine the response to increased entrainment and detrainment.

Global snow mass measurements and the effect of stratigraphic detail on inversion of microwave brightness temperatures

Snow provides large seasonal storage of freshwater, and information about the distribution of snow mass as Snow Water Equivalent (SWE) is important for hydrological planning and detecting climate change impacts. Large regional disagreements remain between estimates from reanalyses, remote sensing and modelling. Assimilating passive microwave information improves SWE estimates in many regions but the assimilation must account for how microwave scattering depends on snow stratigraphy. Physical snow models can estimate snow stratigraphy, but users must consider the computational expense of model complexity versus acceptable errors. Using data from the National Aeronautics and Space Administration Cold Land Processes Experiment (NASA CLPX) and the Helsinki University of Technology (HUT) microwave emission model of layered snowpacks, it is shown that simulations of the brightness temperature difference between 19 GHz and 37 GHz vertically polarised microwaves are consistent with Advanced Microwave Scanning Radiometer-Earth Observing System (AMSR-E) and Special Sensor Microwave Imager (SSM/I) retrievals once known stratigraphic information is used. Simulated brightness temperature differences for an individual snow profile depend on the provided stratigraphic detail. Relative to a profile defined at the 10 cm resolution of density and temperature measurements, the error introduced by simplification to a single layer of average properties increases approximately linearly with snow mass. If this brightness temperature error is converted into SWE using a traditional retrieval method then it is equivalent to ±13 mm SWE (7% of total) at a depth of 100 cm. This error is reduced to ±5.6 mm SWE (3 % of total) for a two-layer model.

Adsorption of organic molecules at the TiO2(110) surface: the effect of van der Waals interactions

Understanding the interaction of organic molecules with TiO2 surfaces is important for a wide range of technological applications. While density functional theory (DFT) calculations can provide valuable insight about these interactions, traditional DFT approaches with local exchange-correlation functionals suffer from a poor description of non-bonding van der Waals (vdW) interactions. We examine here the contribution of vdW forces to the interaction of small organic molecules (methane, methanol, formic acid and glycine) with the TiO2 (110) surface, based on DFT calculations with the optB88-vdW functional. The adsorption geometries and energies at different configurations were also obtained in the standard generalized gradient approximation (GGA-PBE) for comparison. We find that the optB88-vdW consistently gives shorter surface adsorbate-to-surface distances and slightly stronger interactions than PBE for the weak (physisorbed) modes of adsorption. In the case of strongly adsorbed (chemisorbed) molecules both functionals give similar results for the adsorption geometries, and also similar values of the relative energies between different chemisorption modes for each molecule. In particular both functionals predict that dissociative adsorption is more favourable than molecular adsorption for methanol, formic acid and glycine, in general agreement with experiment. The dissociation energies obtained from both functionals are also very similar, indicating that vdW interactions do not affect the thermodynamics of surface deprotonation. However, the optB88-vdW always predicts stronger adsorption than PBE. The comparison of the methanol adsorption energies with values obtained from a Redhead analysis of temperature programmed desorption data suggests that optB88-vdW significantly overestimates the adsorption strength, although we warn about the uncertainties involved in such comparisons.