Excited vibrational state microwave spectra, structure, and force-field of trifluorosilane

The J = 2−1 microwave spectrum of six isotopic species of HSiF3 has been observed and assigned in excited states of five of the six fundamental vibrations. The assignment is based on relative intensities, double resonance experiments, and trial anharmonic force constant calculations. Analysis of the spectra leads to experimental values for five of the constants, all three l-doubling constants qt, one Fermi resonance constant φ233, and one zeta constant. The harmonic force field has been refined to all the available data on vibration wavenumbers, centrifugal distortion constants, and zeta constants. The cubic anharmonic force field has been refined to the data on and qt constants, using two models: a valence force model with two cubic force constants for SiH and SiF stretching, and a more sophisticated model. With the help of these calculations, the following equilibrium structure has been determined: re(SiH) = 1.4468(±5) Å, re(SiF) = 1.5624(±1) Å, HSiF = 110.64(±3)°,

Microwave spectrum of CF3CCH

Attempts to observe ΔK = ±1 transitions in the rotational spectrum of CF3CCH and CF3H in the first excited state of a degenerate vibration, by direct absorption in the Y band and K band regions of the microwave spectrum, have not been successful. In the course of this work the J = 3-2 and 4-3 rotational spectrum of CF3CCH has been observed with higher sensitivity than previously, and from the positions of the vibrational satellites several new rB values have been determined.

The microwave spectrum of thietan-2,2,4,4-d4

The microwave spectrum for thietan-2,2,4,4-d4 is analysed in six of its lowest puckering states and up to J = 25. The close lying pairs of states of vp = 0/1, 2/3 and 4/5 are treated with a vibration-rotation hamiltonian which includes an off-diagonal coupling term in vp. Additional corrections to this coupling term in higher powers of the angular momentum operator are derived and their importance for improving the fit of calculated to observed data is tested. The variation of the centrifugal distortion constants with vp follows the model of Creswell and Mills (1974, J. molec. Spectrosc., 52, 392). A value is determined for the derivative with respect to the puckering coordinate of the ac-component of the inverse moment of inertia tensor.

The microwave spectrum of 1-pyrazoline

The microwave spectrum of 1-pyrazoline has been observed from 18 to 40 GHz in the six lowest states of the ring-puckering vibration. It is an a-type spectrum of a near oblate asymmetric top. Each vibrational state has been fitted to a separate effective Hamiltonian, and the vibrational dependence of both the rotational constants and the quartic centrifugal distortion constants has been observed and analyzed. The v = 0 and 1 states have also been analyzed using a coupled Hamiltonian; this gives consistent results, with an improved fit to the high J data. The preferred choice of Durig et al. [J. Chem. Phys. 52, 6096 (1970)] for the ring-puckering potential is confirmed as essentially correct, but the A and B inertial axes are shown to be interchanged from those assumed by Durig et al. in their analysis of the mid-infrared spectrum.

Microwave spectrum of deuterated silyl isocyanate, SiD3NCO

The microwave spectrum of SiD3NCO has been observed and analyzed for 18 different vibrational states in the ν10 manifold. Some accidental resonances have been observed and analyzed. The vibrational dependence of the rotational and l-doubling constant and centrifugal distortion constant DJK has been successfully interpreted in terms of the two-dimensional anharmonic oscillator model.

Arctic oscillation or North Atlantic oscillation?

The definition and interpretation of the Arctic oscillation (AO) are examined and compared with those of the North Atlantic oscillation (NAO). It is shown that the NAO reflects the correlations between the surface pressure variability at its centers of action, whereas this is not the case for the AO. The NAO pattern can be identified in a physically consistent way in principal component analysis applied to various fields in the Euro-Atlantic region. A similar identification is found in the Pacific region for the Pacific–North American (PNA) pattern, but no such identification is found here for the AO. The AO does reflect the tendency for the zonal winds at 35° and 55°N to anticorrelate in both the Atlantic and Pacific regions associated with the NAO and PNA. Because climatological features in the two ocean basins are at different latitudes, the zonally symmetric nature of the AO does not mean that it represents a simple modulation of the circumpolar flow. An increase in the AO or NAO implies strong, separated tropospheric jets in the Atlantic but a weakened Pacific jet. The PNA has strong related variability in the Pacific jet exit, but elsewhere the zonal wind is similar to that related to the NAO. The NAO-related zonal winds link strongly through to the stratosphere in the Atlantic sector. The PNA-related winds do so in the Pacific, but to a lesser extent. The results suggest that the NAO paradigm may be more physically relevant and robust for Northern Hemisphere variability than is the AO paradigm. However, this does not disqualify many of the physical mechanisms associated with annular modes for explaining the existence of the NAO.

A regime view of the North Atlantic Oscillation and its response to anthropogenic forcing

The distribution of the daily wintertime North Atlantic Oscillation (NAO) index in the 40-yr ECMWF Re-Analysis (ERA-40) is significantly negatively skewed. Dynamical and statistical analyses both suggest that this skewness reflects the presence of two distinct regimes—referred to as “Greenland blocking” and “subpolar jet.” Changes in both the relative occurrence and in the structure of the regimes are shown to contribute to the long-term NAO trend over the ERA-40 period. This is contrasted with the simulation of the NAO in 100-yr control and doubled CO2 integrations of the third climate configuration of the Met Office Unified Model (HadCM3). The model has clear deficiencies in its simulation of the NAO in the control run, so its predictions of future behavior must be treated with caution. However, the subpolar jet regime does become more dominant under anthropogenic forcing and, while this change is small it is clearly statistically significant and does represent a real change in the nature of NAO variability in the model.

Microwave activation of the electro-oxidation of glucose in alkaline media

The oxidation of glucose is a complex process usually requiring catalytically active electrode surfaces or enzyme modified electrodes. In this study the effect of high intensity microwave radiation on the oxidation of glucose in alkaline solution at Au, Cu, and Ni electrodes is reported. Calibration experiments with the Fe(CN)(6)(3-/4-) redox system in aqueous 0.1 M NaOH indicate that strong thermal effects occur at both 50 and 500 mu m diameter electrodes with temperatures reaching 380 K. Extreme mass transport effects with mass transport coefficients of k(mt) > 0.01 m s(-1) (or k(mt) > 1.0 cm s(-1)) are observed at 50 mu m diameter electrodes in the presence of microwaves. The electrocatalytic oxidation of glucose at 500 mu m diameter Au, Cu, or Ni electrodes immersed in 0.1 M NaOH and in the presence of microwave radiation is shown to be dominated by kinetic control. The magnitude of glucose oxidation currents at Cu electrodes is shown to depend on the thickness of a pre-formed oxide layer. At 50 mu m diameter Au, Cu, or Ni electrodes microwave enhanced current densities are generally higher, but only at Au electrodes is a significantly increased rate for the electrocatalytic oxidation of glucose to gluconolactone observed. This rate enhancement appears to be independent of temperature but microwave intensity dependent, and therefore non-thermal in nature. Voltammetric currents observed at Ni electrodes in the presence of microwaves show the best correlation with glucose concentration and are therefore analytically most useful.

Microwave activation of the electro-oxidation of glucose in alkaline media

The oxidation of glucose is a complex process usually requiring catalytically active electrode surfaces or enzyme-modified electrodes. In this study the effect of high intensity microwave radiation on the oxidation of glucose in alkaline solution at Au, Cu, and Ni electrodes is reported. Calibration experiments with the Fe(CN)63–/4– redox system in aqueous 0.1 M NaOH indicate that strong thermal effects occur at both 50 and 500 µm diameter electrodes with temperatures reaching 380 K. Extreme mass transport effects with mass transport coefficients of kmt > 0.01 m s–1(or kmt > 1.0 cm s–1) are observed at 50 µm diameter electrodes in the presence of microwaves. The electrocatalytic oxidation of glucose at 500 µm diameter Au, Cu, or Ni electrodes immersed in 0.1 M NaOH and in the presence of microwave radiation is shown to be dominated by kinetic control. The magnitude of glucose oxidation currents at Cu electrodes is shown to depend on the thickness of a pre-formed oxide layer. At 50 µm diameter Au, Cu, or Ni electrodes microwave enhanced current densities are generally higher, but only at Au electrodes is a significantly increased rate for the electrocatalytic oxidation of glucose to gluconolactone observed. This rate enhancement appears to be independent of temperature but microwave intensity dependent, and therefore non-thermal in nature. Voltammetric currents observed at Ni electrodes in the presence of microwaves show the best correlation with glucose concentration and are therefore analytically most useful.

Precipitation and latent heating distributions from satellite passive microwave radiometry. Part I: improved method and uncertainties

A revised Bayesian algorithm for estimating surface rain rate, convective rain proportion, and latent heating profiles from satellite-borne passive microwave radiometer observations over ocean backgrounds is described. The algorithm searches a large database of cloud-radiative model simulations to find cloud profiles that are radiatively consistent with a given set of microwave radiance measurements. The properties of these radiatively consistent profiles are then composited to obtain best estimates of the observed properties. The revised algorithm is supported by an expanded and more physically consistent database of cloud-radiative model simulations. The algorithm also features a better quantification of the convective and nonconvective contributions to total rainfall, a new geographic database, and an improved representation of background radiances in rain-free regions. Bias and random error estimates are derived from applications of the algorithm to synthetic radiance data, based upon a subset of cloud-resolving model simulations, and from the Bayesian formulation itself. Synthetic rain-rate and latent heating estimates exhibit a trend of high (low) bias for low (high) retrieved values. The Bayesian estimates of random error are propagated to represent errors at coarser time and space resolutions, based upon applications of the algorithm to TRMM Microwave Imager (TMI) data. Errors in TMI instantaneous rain-rate estimates at 0.5°-resolution range from approximately 50% at 1 mm h−1 to 20% at 14 mm h−1. Errors in collocated spaceborne radar rain-rate estimates are roughly 50%–80% of the TMI errors at this resolution. The estimated algorithm random error in TMI rain rates at monthly, 2.5° resolution is relatively small (less than 6% at 5 mm day−1) in comparison with the random error resulting from infrequent satellite temporal sampling (8%–35% at the same rain rate). Percentage errors resulting from sampling decrease with increasing rain rate, and sampling errors in latent heating rates follow the same trend. Averaging over 3 months reduces sampling errors in rain rates to 6%–15% at 5 mm day−1, with proportionate reductions in latent heating sampling errors.

Bayesian retrieval of complete posterior PDFs of oceanic rain rate from microwave observations

A new Bayesian algorithm for retrieving surface rain rate from Tropical Rainfall Measuring Mission (TRMM) Microwave Imager (TMI) over the ocean is presented, along with validations against estimates from the TRMM Precipitation Radar (PR). The Bayesian approach offers a rigorous basis for optimally combining multichannel observations with prior knowledge. While other rain-rate algorithms have been published that are based at least partly on Bayesian reasoning, this is believed to be the first self-contained algorithm that fully exploits Bayes’s theorem to yield not just a single rain rate, but rather a continuous posterior probability distribution of rain rate. To advance the understanding of theoretical benefits of the Bayesian approach, sensitivity analyses have been conducted based on two synthetic datasets for which the “true” conditional and prior distribution are known. Results demonstrate that even when the prior and conditional likelihoods are specified perfectly, biased retrievals may occur at high rain rates. This bias is not the result of a defect of the Bayesian formalism, but rather represents the expected outcome when the physical constraint imposed by the radiometric observations is weak owing to saturation effects. It is also suggested that both the choice of the estimators and the prior information are crucial to the retrieval. In addition, the performance of the Bayesian algorithm herein is found to be comparable to that of other benchmark algorithms in real-world applications, while having the additional advantage of providing a complete continuous posterior probability distribution of surface rain rate.

The impact of finer-resolution air-sea coupling on the intraseasonal oscillation of the Indian monsoon

The new HadKPP atmosphere–ocean coupled model is described and then used to determine the effects of sub-daily air–sea coupling and fine near-surface ocean vertical resolution on the representation of the Northern Hemisphere summer intra-seasonal oscillation. HadKPP comprises the Hadley Centre atmospheric model coupled to the K Profile Parameterization ocean-boundary-layer model. Four 30-member ensembles were performed that varied in oceanic vertical resolution between 1 m and 10 m and in coupling frequency between 3 h and 24 h. The 10 m, 24 h ensemble exhibited roughly 60% of the observed 30–50 day variability in sea-surface temperatures and rainfall and very weak northward propagation. Enhancing either only the vertical resolution or only the coupling frequency produced modest improvements in variability and only a standing intra-seasonal oscillation. Only the 1 m, 3 h configuration generated organized, northward-propagating convection similar to observations. Sub-daily surface forcing produced stronger upper-ocean temperature anomalies in quadrature with anomalous convection, which likely affected lower-atmospheric stability ahead of the convection, causing propagation. Well-resolved air–sea coupling did not improve the eastward propagation of the boreal summer intra-seasonal oscillation in this model. Upper-ocean vertical mixing and diurnal variability in coupled models must be improved to accurately resolve and simulate tropical sub-seasonal variability. In HadKPP, the mere presence of air–sea coupling was not sufficient to generate an intra-seasonal oscillation resembling observations.

A review on Northern Hemisphere sea-ice, storminess and the North Atlantic Oscillation: observations and projected changes

The Arctic has undergone substantial changes over the last few decades in various cryospheric and derivative systems and processes. Of these, the Arctic sea ice regime has seen some of the most rapid change and is one of the most visible markers of Arctic change outside the scientific community. This has drawn considerable attention not only from the natural sciences, but increasingly, from the political and commercial sectors as they begin to grapple with the problems and opportunities that are being presented. The possible impacts of past and projected changes in Arctic sea ice, especially as it relates to climatic response, are of particular interest and have been the subject of increasing research activity. A review of the current knowledge of the role of sea ice in the climate system is therefore timely. We present a review that examines both the current state of understanding, as regards the impacts of sea-ice loss observed to date, and climate model projections, to highlight hypothesised future changes and impacts on storm tracks and the North Atlantic Oscillation. Within the broad climate-system perspective, the topics of storminess and large-scale variability will be specifically considered. We then consider larger-scale impacts on the climatic system by reviewing studies that have focused on the interaction between sea-ice extent and the North Atlantic Oscillation. Finally, an overview of the representation of these topics in the literature in the context of IPCC climate projections is presented. While most agree on the direction of Arctic sea-ice change, the rates amongst the various projections vary greatly. Similarly, the response of storm tracks and climate variability are uncertain, exacerbated possibly by the influence of other factors. A variety of scientific papers on the relationship between sea-ice changes and atmospheric variability have brought to light important aspects of this complex topic. Examples are an overall reduction in the number of Arctic winter storms, a northward shift of mid-latitude winter storms in the Pacific and a delayed negative NAO-like response in autumn/winter to a reduced Arctic sea-ice cover (at least in some months). This review paper discusses this research and the disagreements, bringing about a fresh perspective on this issue.