Relationship between phonons and thermal expansion in Zn(CN)2 and Ni(CN)2 from inelastic neutron scattering and ab initio calculations

Zn(CN)2 and Ni(CN)2 are known for exhibiting anomalous thermal expansion over a wide temperature range. The volume thermal expansion coefficient for the cubic, three dimensionally connected material, Zn(CN)2, is negative (alpha(V) = −51  10(-6) K-1) while for Ni(CN)2, a tetragonal material, the thermal expansion coefficient is negative in the two dimensionally connected sheets (alpha(a) = −7  10(-6) K-1), but the overall thermal expansion coefficient is positive (alpha(V) = 48  10(-6) K-1). We have measured the temperature dependence of phonon spectra in these compounds and analyzed them using ab initio calculations. The spectra of the two compounds show large differences that cannot be explained by simple mass renormalization of the modes involving Zn (65.38 amu) and Ni (58.69 amu) atoms. This reflects the fact that the structure and bonding are quite different in the two compounds. The calculated pressure dependence of the phonon modes and of the thermal expansion coefficient, alpha(V), are used to understand the anomalous behavior in these compounds. Our ab initio calculations indicate that phonon modes of energy approx. 2 meV are major contributors to negative thermal expansion (NTE) in both the compounds. The low-energy modes of approx.8 and 13 meV in Zn(CN)2 also contribute significantly to the NTE in Zn(CN)2 and Ni(CN)2, respectively. The measured temperature dependence of the phonon spectra has been used to estimate the total anharmonicity of both compounds. For Zn(CN)2, the temperature-dependent measurements (total anharmonicity), along with our previously reported pressure dependence of the phonon spectra (quasiharmonic), is used to separate the explicit temperature effect at constant volume (intrinsic anharmonicity).

Thermal expansion of deuterated hopeite, Zn-3(PO4)(2)center dot 4D(2)O

The lattice parameters extracted from Lebail analysis of neutron powder diffraction data collected between 2 and 300 K have been used to calculate the temperature evolution of the thermal expansion tensor for hopeite, Zn-3(PO4)(2)center dot 2H(2)O, Pnma,Z=4with a= 10.6065(4) angstrom, b = 18.2977(4) angstrom, c= 5.0257(2) A at 275 K. The a lattice parameter shows a negative thermal expansion, the b lattice parameter appears to saturate at 275 K while the c lattice parameter has a more typical positive thermal expansion. At 275 K, the magnitudes of the thermal expansion coefficients are alpha(a) = -1. 1(4) x 10(-5) K-1, alpha(b) = 2.4(9) x 10(-6) K-1 and alpha(c) = 3.6(2) x 10(-1) K-1. Under the conditions of these experiments, hopeite begins to dehydrate to the dihydrate between 300 and 325 K, and between 480 and 500 K the monohydrate is formed. The thermal expansion of the dihydrate has been calculated between 335 and 480 and at 480 K the magnitudes of the thermal expansion coefficients are alpha(a) = 1(2) x 10(-5) K-1, alpha(b) = 4(l) x 10(-6) K-1, alpha(c) = 4(2) x 10(-5) K-1, alpha(beta) = 1 (1) x 10(-1) K-1, and alpha(v) = 2(2) x 10(-1) K-1. The thermal expansion of hopeite is described in terms of its crystal structure and possible dehydration mechanisms for the alpha and beta modifications of hopeite are discussed.

Krakatoa lives: The effect of volcanic eruptions on ocean heat content and thermal expansion

A suite of climate model experiments indicates that 20th Century increases in ocean heat content and sea-level ( via thermal expansion) were substantially reduced by the 1883 eruption of Krakatoa. The volcanically-induced cooling of the ocean surface is subducted into deeper ocean layers, where it persists for decades. Temporary reductions in ocean heat content associated with the comparable eruptions of El Chichon ( 1982) and Pinatubo ( 1991) were much shorter lived because they occurred relative to a non-stationary background of large, anthropogenically-forced ocean warming. Our results suggest that inclusion of the effects of Krakatoa ( and perhaps even earlier eruptions) is important for reliable simulation of 20th century ocean heat uptake and thermal expansion. Inter-model differences in the oceanic thermal response to Krakatoa are large and arise from differences in external forcing, model physics, and experimental design. Systematic experimentation is required to quantify the relative importance of these factors. The next generation of historical forcing experiments may require more careful treatment of pre-industrial volcanic aerosol loadings.

A differential thermal expansion approach to crystal structure determination from powder diffraction data

Differential thermal expansion over the range 90-210 K has been applied successfully to determine the crystal structure of chlorothiazide from synchrotron powder diffraction data using direct methods. Key to the success of the approach is the use of a multi-data-set Pawley refinement to extract a set of reflection intensities that is more 'single-crystal-like' than those extracted from a single data set. The improvement in reflection intensity estimates is quantified by comparison with reference single-crystal intensities. (C) 2008 International Union of Crystallography Printed in Singapore - all rights reserved

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.

Local and average structure in zinc cyanide: towards an understanding of the atomistic origin of negative thermal expansion

Neutron diffraction at 11.4 and 295 K and solid-state 67Zn NMR are used to determine both the local and average structures in the disordered, negative thermal expansion (NTE) material, Zn(CN)2. Solid-state NMR not only confirms that there is head-to-tail disorder of the C≡N groups present in the solid, but yields information about the relative abundances of the different Zn(CN)4-n(NC)n tetrahedral species, which do not follow a simple binomial distribution. The Zn(CN)4 and Zn(NC)4 species occur with much lower probabilities than are predicted by binomial theory, supporting the conclusion that they are of higher energy than the other local arrangements. The lowest energy arrangement is Zn(CN)2(NC)2. The use of total neutron diffraction at 11.4 K, with analysis of both the Bragg diffraction and the derived total correlation function, yields the first experimental determination of the individual Zn−N and Zn−C bond lengths as 1.969(2) and 2.030(2) Å, respectively. The very small difference in bond lengths, of ~0.06 Å, means that it is impossible to obtain these bond lengths using Bragg diffraction in isolation. Total neutron diffraction also provides information on both the average and local atomic displacements responsible for NTE in Zn(CN)2. The principal motions giving rise to NTE are shown to be those in which the carbon and nitrogen atoms within individual Zn−C≡N−Zn linkages are displaced to the same side of the Zn···Zn axis. Displacements of the carbon and nitrogen atoms to opposite sides of the Zn···Zn axis, suggested previously in X-ray studies as being responsible for NTE behavior, in fact make negligible contribution at temperatures up to 295 K.

Climate models without pre-industrial volcanic forcing underestimate historical ocean thermal expansion

Episodic explosive volcanic eruptions are a natural part of the climate system but are often omitted from atmosphere-ocean general circulation model (AOGCM) preindustrial spin-up and control experiments. This omission imposes a negative bias on ocean heat uptake in simulations of the historical period. In models of a range of complexity, we find that global-mean sea level rise due to thermal expansion during the last ∼ 150 years is consequently underestimated by 5–30 mm, which is a substantial proportion of the model mean of 50 mm in Coupled Model Intercomparison Project Phase 3 AOGCMs with anthropogenic forcing only, and is therefore important in accounting for 20th century sea level rise. We test and recommend a procedure for removing the bias.

CO2 emission estimation in the urban environment: measurement of the CO2 storage term

Eddy covariance has been used in urban areas to evaluate the net exchange of CO2 between the surface and the atmosphere. Typically, only the vertical flux is measured at a height 2–3 times that of the local roughness elements; however, under conditions of relatively low instability, CO2 may accumulate in the airspace below the measurement height. This can result in inaccurate emissions estimates if the accumulated CO2 drains away or is flushed upwards during thermal expansion of the boundary layer. Some studies apply a single height storage correction; however, this requires the assumption that the response of the CO2 concentration profile to forcing is constant with height. Here a full seasonal cycle (7th June 2012 to 3rd June 2013) of single height CO2 storage data calculated from concentrations measured at 10 Hz by open path gas analyser are compared to a data set calculated from a concurrent switched vertical profile measured (2 Hz, closed path gas analyser) at 10 heights within and above a street canyon in central London. The assumption required for the former storage determination is shown to be invalid. For approximately regular street canyons at least one other measurement is required. Continuous measurements at fewer locations are shown to be preferable to a spatially dense, switched profile, as temporal interpolation is ineffective. The majority of the spectral energy of the CO2 storage time series was found to be between 0.001 and 0.2 Hz (500 and 5 s respectively); however, sampling frequencies of 2 Hz and below still result in significantly lower CO2 storage values. An empirical method of correcting CO2 storage values from under-sampled time series is proposed.

Understanding mixing efficiency in the oceans. Do the nonlinearities of the equation of state matter?

There exist two central measures of turbulent mixing in turbulent stratified fluids that are both caused by molecular diffusion: 1) the dissipation rate D(APE) of available potential energy APE; 2) the turbulent rate of change Wr, turbulent of background gravitational potential energy GPEr. So far, these two quantities have often been regarded as the same energy conversion, namely the irreversible conversion of APE into GPEr, owing to the well known exact equality D(APE)=Wr, turbulent for a Boussinesq fluid with a linear equation of state. Recently, however, Tailleux (2009) pointed out that the above equality no longer holds for a thermally-stratified compressible, with the ratio ξ=Wr, turbulent/D(APE) being generally lower than unity and sometimes even negative for water or seawater, and argued that D(APE) and Wr, turbulent actually represent two distinct types of energy conversion, respectively the dissipation of APE into one particular subcomponent of internal energy called the "dead" internal energy IE0, and the conversion between GPEr and a different subcomponent of internal energy called "exergy" IEexergy. In this paper, the behaviour of the ratio ξ is examined for different stratifications having all the same buoyancy frequency N vertical profile, but different vertical profiles of the parameter Υ=α P/(ρCp), where α is the thermal expansion coefficient, P the hydrostatic pressure, ρ the density, and Cp the specific heat capacity at constant pressure, the equation of state being that for seawater for different particular constant values of salinity. It is found that ξ and Wr, turbulent depend critically on the sign and magnitude of dΥ/dz, in contrast with D(APE), which appears largely unaffected by the latter. These results have important consequences for how the mixing efficiency should be defined and measured in practice, which are discussed.

Simulated global-mean sea level changes over the last half-millennium

Simulations of the last 500 yr carried out using the Third Hadley Centre Coupled Ocean-Atmosphere GCM (HadCM3) with anthropogenic and natural (solar and volcanic) forcings have been analyzed. Global-mean surface temperature change during the twentieth century is well reproduced. Simulated contributions to global-mean sea level rise during recent decades due to thermal expansion (the largest term) and to mass loss from glaciers and ice caps agree within uncertainties with observational estimates of these terms, but their sum falls short of the observed rate of sea level rise. This discrepancy has been discussed by previous authors; a completely satisfactory explanation of twentieth-century sea level rise is lacking. The model suggests that the apparent onset of sea level rise and glacier retreat during the first part of the nineteenth century was due to natural forcing. The rate of sea level rise was larger during the twentieth century than during the previous centuries because of anthropogenic forcing, but decreasing natural forcing during the second half of the twentieth century tended to offset the anthropogenic acceleration in the rate. Volcanic eruptions cause rapid falls in sea level, followed by recovery over several decades. The model shows substantially less decadal variability in sea level and its thermal expansion component than twentieth-century observations indicate, either because it does not generate sufficient ocean internal variability, or because the observational analyses overestimate the variability.

Understanding projections of sea level rise in a Hadley Centre coupled climate model

Sea level changes resulting from CO2-induced climate changes in ocean density and circulation have been investigated in a series of idealised experiments with the Hadley Centre HadCM3 AOGCM. Changes in the mass of the ocean were not included. In the global mean, salinity changes have a negligible effect compared with the thermal expansion of the ocean. Regionally, sea level changes are projected to deviate greatly from the global mean (standard deviation is 40% of the mean). Changes in surface fluxes of heat, freshwater and wind stress are all found to produce significant and distinct regional sea level changes, wind stress changes being the most important and the cause of several pronounced local features, while heat and freshwater flux changes affect large parts of the North Atlantic and Southern Ocean. Regional change is related mainly to density changes, with a relatively small contribution in mid and high latitudes from change in the barotropic circulation. Regional density change has an important contribution from redistribution of ocean heat content. In general, unlike in the global mean, the regional pattern of sea level change due to density change appears to be influenced almost as much by salinity changes as by temperature changes, often in opposition. Such compensation is particularly marked in the North Atlantic, where it is consistent with recent observed changes. We suggest that density compensation is not a property of climate change specifically, but a general behavior of the ocean.

Aperiodicity, structure, and dynamics in Ni(CN)(2)

By combining the results of both x-ray diffraction and neutron total-scattering experiments, we show that Ni(CN)(2) exhibits long-range structural order only in two dimensions, with no true periodicity perpendicular to its gridlike layers. Reverse Monte Carlo analysis gives an experimental distinction between M-C and M-N bond lengths in a homometallic cyanide framework and identifies the vibrational modes responsible for anomalous positive and negative thermal expansion in the title compound.

Structure of AuCN determined from total neutron diffraction

The structure of gold cyanide, AuCN, has been determined at 10 and 300 K using total neutron diffraction. The structure consists of infinite -Au-(CN)-Au-(CN)-Au-(CN)- linear chains, hexagonally packed, with the gold atoms in sheets. The Au-C and Au-N bond lengths are found to be identical, with d(Au-C/N) = 1.9703(5) Angstrom at 300 K. This work supersedes a previous study, by others, which used Rietveld analysis of neutron Bragg diffraction in isolation, and found these bonds to have significantly different lengths (Deltad = 0.24 Angstrom) at 300 K. The total correlation function, T(r), at 10 and 300 K, has been modeled using information derived from total diffraction. The broadening of inter- and intrachain correlations differs markedly due to random displacements of the chains in the direction of the chain axes. This is a consequence of the relatively weak bonding between the chains. An explanation for the negative thermal expansion in the c-direction, which occurs between 10 and 300 K, is presented.

Comparison of results from several AOGCMs for global and regional sea-level change 1900-2100

Sea-level rise is an important aspect of climate change because of its impact on society and ecosystems. Here we present an intercomparison of results from ten coupled atmosphere-ocean general circulation models (AOGCMs) for sea-level changes simulated for the twentieth century and projected to occur during the twenty first century in experiments following scenario IS92a for greenhouse gases and sulphate aerosols. The model results suggest that the rate of sea-level rise due to thermal expansion of sea water has increased during the twentieth century, but the small set of tide gauges with long records might not be adequate to detect this acceleration. The rate of sea-level rise due to thermal expansion continues to increase throughout the twenty first century, and the projected total is consequently larger than in the twentieth century; for 1990-2090 it amounts to 0.20-0.37 in. This wide range results from systematic uncertainty in modelling of climate change and of heat uptake by the ocean. The AOGCMs agree that sea-level rise is expected to be geographically non-uniform, with some regions experiencing as much as twice the global average, and others practically zero, but they do not agree about the geographical pattern. The lack of agreement indicates that we cannot currently have confidence in projections of local sea- level changes, and reveals a need for detailed analysis and intercomparison in order to understand and reduce the disagreements.

Understanding and projecting sea level change

There is intense scientific and public interest in the Intergovernmental Panel on Climate Change (IPCC) projections of sea level for the twenty-first century and beyond. The Fourth Assessment Report (AR4) projections, obtained by applying standard methods to the results of the World Climate Research Programme Coupled Model Experiment, includes estimates of ocean thermal expansion, the melting of glaciers and ice caps (G&ICs), increased melting of the Greenland Ice Sheet, and increased precipitation over Greenland and Antarctica, partially offsetting other contributions. The AR4 recognized the potential for a rapid dynamic ice sheet response but robust methods for quantifying it were not available. Illustrative scenarios suggested additional sea level rise on the order of 10 to 20 cm or more, giving a wide range in the global averaged projections of about 20 to 80 cm by 2100. Currently, sea level is rising at a rate near the upper end of these projections. Since publication of the AR4 in 2007, biases in historical ocean temperature observations have been identified and significantly reduced, resulting in improved estimates of ocean thermal expansion. Models that include all climate forcings are in good agreement with these improved observations and indicate the importance of stratospheric aerosol loadings from volcanic eruptions. Estimates of the volumes of G&ICs and their contributions to sea level rise have improved. Results from recent (but possibly incomplete) efforts to develop improved ice sheet models should be available for the 2013 IPCC projections. Improved understanding of sea level rise is paving the way for using observations to constrain projections. Understanding of the regional variations in sea level change as a result of changes in ocean properties, wind-stress patterns, and heat and freshwater inputs into the ocean is improving. Recently, estimates of sea level changes resulting from changes in Earth's gravitational field and the solid Earth response to changes in surface loading have been included in regional projections. While potentially valuable, semi-empirical models have important limitations, and their projections should be treated with caution