Uncertainties in future projections of extreme precipitation in the Indian monsoon region

Uncertainties in changes to the spatial distribution and magnitude of the heaviest extremes of daily monsoon rainfall over India are assessed in the doubled CO2 climate change scenarios in the IPCC Fourth Assessment Report. Results show diverse changes to the spatial pattern of the 95th and 99th subseasonal percentiles, which are strongly tied to the mean precipitation change during boreal summer. In some models, the projected increase in heaviest rainfall over India at CO2 doubling is entirely predictable based upon the surface warming and the Clausius–Clapeyron relation, a result which may depend upon the choice of convection scheme. Copyright © 2009 Royal Meteorological Society and Crown Copyright

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.

The potential to narrow uncertainty in projections of regional precipitation change

We separate and quantify the sources of uncertainty in projections of regional (*2,500 km) precipitation changes for the twenty-first century using the CMIP3 multi-model ensemble, allowing a direct comparison with a similar analysis for regional temperature changes. For decadal means of seasonal mean precipitation, internal variability is the dominant uncertainty for predictions of the first decade everywhere, and for many regions until the third decade ahead. Model uncertainty is generally the dominant source of uncertainty for longer lead times. Scenario uncertainty is found to be small or negligible for all regions and lead times, apart from close to the poles at the end of the century. For the global mean, model uncertainty dominates at all lead times. The signal-to-noise ratio (S/N) of the precipitation projections is highest at the poles but less than 1 almost everywhere else, and is far lower than for temperature projections. In particular, the tropics have the highest S/N for temperature, but the lowest for precipitation. We also estimate a ‘potential S/N’ by assuming that model uncertainty could be reduced to zero, and show that, for regional precipitation, the gains in S/N are fairly modest, especially for predictions of the next few decades. This finding suggests that adaptation decisions will need to be made in the context of high uncertainty concerning regional changes in precipitation. The potential to narrow uncertainty in regional temperature projections is far greater. These conclusions on S/N are for the current generation of models; the real signal may be larger or smaller than the CMIP3 multi-model mean. Also note that the S/N for extreme precipitation, which is more relevant for many climate impacts, may be larger than for the seasonal mean precipitation considered here.

The puckering coordinate in oxetane

The recently determined apucker(xz) = ∂Ixz/∂Qpucker constants for five isotopic species of oxetane have been interpreted quantitatively by allowing the ring-puckering normal coordinate to contain a small amount of methylene rocking and twisting motion. The observed data are most closely reproduced by assuming a methylene rock angle of about 3° and a twist angle for the -methylene groups of about 1° at the equilibrium conformation of the ring.

ASYM20: a program for force constant and normal coordinate calculations, with a critical review of the theory involved

The theory of harmonic force constant refinement calculations is reviewed, and a general-purpose program for force constant and normal coordinate calculations is described. The program, called ASYM20. is available through Quantum Chemistry Program Exchange. It will work on molecules of any symmetry containing up to 20 atoms and will produce results on a series of isotopomers as desired. The vibrational secular equations are solved in either nonredundant valence internal coordinates or symmetry coordinates. As well as calculating the (harmonic) vibrational wavenumbers and normal coordinates, the program will calculate centrifugal distortion constants, Coriolis zeta constants, harmonic contributions to the α′s. root-mean-square amplitudes of vibration, and other quantities related to gas electron-diffraction studies and thermodynamic properties. The program will work in either a predict mode, in which it calculates results from an input force field, or in a refine mode, in which it refines an input force field by least squares to fit observed data on the quantities mentioned above. Predicate values of the force constants may be included in the data set for a least-squares refinement. The program is written in FORTRAN for use on a PC or a mainframe computer. Operation is mainly controlled by steering indices in the input data file, but some interactive control is also implemented.

The potential to narrow uncertainty in projections of stratospheric ozone over the 21st century

Future stratospheric ozone concentrations will be determined both by changes in the concentration of ozone depleting substances (ODSs) and by changes in stratospheric and tropospheric climate, including those caused by changes in anthropogenic greenhouse gases (GHGs). Since future economic development pathways and resultant emissions of GHGs are uncertain, anthropogenic climate change could be a significant source of uncertainty for future projections of stratospheric ozone. In this pilot study, using an "ensemble of opportunity" of chemistry-climate model (CCM) simulations, the contribution of scenario uncertainty from different plausible emissions pathways for ODSs and GHGs to future ozone projections is quantified relative to the contribution from model uncertainty and internal variability of the chemistry-climate system. For both the global, annual mean ozone concentration and for ozone in specific geographical regions, differences between CCMs are the dominant source of uncertainty for the first two-thirds of the 21st century, up-to and after the time when ozone concentrations return to 1980 values. In the last third of the 21st century, dependent upon the set of greenhouse gas scenarios used, scenario uncertainty can be the dominant contributor. This result suggests that investment in chemistry-climate modelling is likely to continue to refine projections of stratospheric ozone and estimates of the return of stratospheric ozone concentrations to pre-1980 levels.

A case of four-coordinate silver(I) adopting a high energy planar geometry. Experiment and theory

The ligands PhL and MeL are obtained by condensing 2-formylpyridine with benzil dihydrazone and diacetyl dihydrazone, respectively, in 2: 1 molar proportion. With silver( I), PhL yields a double-stranded dinuclear cationic helicate 1 in which the metal is tetrahedral but MeL gives a cationic one-dimensional polymeric complex 2 where silver( I) is distorted square planar and the ligand backbone is nearly planar. In both complexes, metal: ligand ratio is 1: 1. Ab initio calculations on the ligands at the HF/6-31+G* level reveal that while PhL strongly prefers a helical conformation, MeL has a natural inclination to remain in a planar conformation. Density functional theory calculations on model silver( I) complexes show that formation of the linear polymer in the case of MeL is also an important factor in imposing the planar geometry of Ag(I) in 2.

An eight-coordinate mononuclear double helical complex

From the reaction of Cd(CH3COO)(2)(.)2H(2)O with the 1:2 condensate (L) of benzil dihydrazone and 2-acetylpyridine, [CdL(CH3COO)(H2O)]PF(6)(.)3H(2)O (1) is isolated by adding NH4PF6. L reacts with Cd(ClO4)(2)(.)xH(2)O to yield [CdL2](ClO4)(2). 0.5H(2)O (2). The yellowish complexes 1 and 2 are characterized by NMR and single-crystal X-ray diffraction. 1 is found to be a seven-coordinate single helical complex having a (CdN4O3)-N-II core and homoleptic 2 an eight-coordinate double helical complex with a (CdN8)-N-II core. (c) Wiley-VCH Verlag GmbH & Co.