Unusual isotope effect in the reaction of chlorosilylene with trimethylsilane-1-d: Absolute rate studies and quantum chemical and Rice–Ramsperger–Kassel–Marcus calculations provide strong evidence for the involvement of an intermediate complex

Time-resolved studies of chlorosilylene, ClSiH, generated by the 193 nm laser flash photolysis of 1-chloro-1- silacyclopent-3-ene, have been carried out to obtain rate constants for its bimolecular reaction with trimethylsilane-1-d, Me3SiD, in the gas phase. The reaction was studied at total pressures up to 100 Torr (with and without added SF6) over the temperature range of 295−407 K. The rate constants were found to be pressure independent and gave the following Arrhenius equation: log[(k/(cm3 molecule−1 s−1)] = (−13.22 ± 0.15) + [(13.20 ± 1.00) kJ mol−1]/(RT ln 10). When compared with previously published kinetic data for the reaction of ClSiH with Me3SiH, kinetic isotope effects, kD/kH, in the range from 7.4 (297 K) to 6.4 (407 K) were obtained. These far exceed values of 0.4−0.5 estimated for a single-step insertion process. Quantum chemical calculations (G3MP2B3 level) confirm not only the involvement of an intermediate complex, but also the existence of a low-energy internal isomerization pathway which can scramble the D and H atom labels. By means of Rice−Ramsperger−Kassel−Marcus modeling and a necessary (but small) refinement of the energy surface, we have shown that this mechanism can reproduce closely the experimental isotope effects. These findings provide the first experimental evidence for the isomerization pathway and thereby offer the most concrete evidence to date for the existence of intermediate complexes in the insertion reactions of silylenes.

The maximum rate of mammal evolution

How fast can a mammal evolve from the size of a mouse to the size of an elephant? Achieving such a large transformation calls for major biological reorganization. Thus, the speed at which this occurs has important implications for extensive faunal changes, including adaptive radiations and recovery from mass extinctions. To quantify the pace of large-scale evolution we developed a metric, clade maximum rate, which represents the maximum evolutionary rate of a trait within a clade. We applied this metric to body mass evolution in mammals over the last 70 million years, during which multiple large evolutionary transitions occurred in oceans and on continents and islands. Our computations suggest that it took a minimum of 1.6, 5.1, and 10 million generations for terrestrial mammal mass to increase 100-, and 1,000-, and 5,000- fold, respectively. Values for whales were down to half the length (i.e., 1.1, 3, and 5 million generations), perhaps due to the reduced mechanical constraints of living in an aquatic environment. When differences in generation time are considered, we find an exponential increase in maximum mammal body mass during the 35 million years following the Cretaceous–Paleogene (K–Pg) extinction event. Our results also indicate a basic asymmetry in macroevolution: very large decreases (such as extreme insular dwarfism) can happen at more than 10 times the rate of increases. Our findings allow more rigorous comparisons of microevolutionary and macroevolutionary patterns and processes. Keywords: haldanes, biological time, scaling, pedomorphosis

Growth rate and vertical propagation of the initial error in baroclinic models

The present study investigates the growth of error in baroclinic waves. It is found that stable or neutral waves are particularly sensitive to errors in the initial condition. Short stable waves are mainly sensitive to phase errors and the ultra long waves to amplitude errors. Analysis simulation experiments have indicated that the amplitudes of the very long waves become usually too small in the free atmosphere, due to the sparse and very irregular distribution of upper air observations. This also applies to the four-dimensional data assimilation experiments, since the amplitudes of the very long waves are usually underpredicted. The numerical experiments reported here show that if the very long waves have these kinds of amplitude errors in the upper troposphere or lower stratosphere the error is rapidly propagated (within a day or two) to the surface and to the lower troposphere.

Model-measurement comparison of mesospheric temperature inversions, and a simple theory for their occurrence

Mesospheric temperature inversions are well established observed phenomena, yet their properties remain the subject of ongoing research. Comparisons between Rayleigh-scatter lidar temperature measurements obtained by the University of Western Ontario's Purple Crow Lidar (42.9°N, 81.4°W) and the Canadian Middle Atmosphere Model are used to quantify the statistics of inversions. In both model and measurements, inversions occur most frequently in the winter and exhibit an average amplitude of ∼10 K. The model exhibits virtually no inversions in the summer, while the measurements show a strongly reduced frequency of occurrence with an amplitude about half that in the winter. A simple theory of mesospheric inversions based on wave saturation is developed, with no adjustable parameters. It predicts that the environmental lapse rate must be less than half the adiabatic lapse rate for an inversion to form, and it predicts the ratio of the inversion amplitude and thickness as a function of environmental lapse rate. Comparison of this prediction to the actual amplitude/thickness ratio using the lidar measurements shows good agreement between theory and measurements.

CP-OQAM-OFDM based SC-FDMA: adjustable user bandwidth and space-time coding

The discrete Fourier transmission spread OFDM DFTS-OFDM) based single-carrier frequency division multiple access (SC-FDMA) has been widely adopted due to its lower peak-to-average power ratio (PAPR) of transmit signals compared with OFDM. However, the offset modulation, which has lower PAPR than general modulation, cannot be directly applied into the existing SC-FDMA. When pulse-shaping filters are employed to further reduce the envelope fluctuation of transmit signals of SC-FDMA, the spectral efficiency degrades as well. In order to overcome such limitations of conventional SC-FDMA, this paper for the first time investigated cyclic prefixed OQAMOFDM (CP-OQAM-OFDM) based SC-FDMA transmission with adjustable user bandwidth and space-time coding. Firstly, we propose CP-OQAM-OFDM transmission with unequally-spaced subbands. We then apply it to SC-FDMA transmission and propose a SC-FDMA scheme with the following features: a) the transmit signal of each user is offset modulated single-carrier with frequency-domain pulse-shaping; b) the bandwidth of each user is adjustable; c) the spectral efficiency does not decrease with increasing roll-off factors. To combat both inter-symbolinterference and multiple access interference in frequencyselective fading channels, a joint linear minimum mean square error frequency domain equalization using a prior information with low complexity is developed. Subsequently, we construct space-time codes for the proposed SC-FDMA. Simulation results confirm the powerfulness of the proposed CP-OQAM-OFDM scheme (i.e., effective yet with low complexity).

Measuring large topographic change with InSAR: lava thicknesses, extrusion rate and subsidence rate at Santiaguito volcano, Guatemala

Lava flows can produce changes in topography on the order of 10s-100s of metres. A knowledge of the resulting volume change provides evidence about the dynamics of an eruption. We present a method to measure topographic changes from the differential InSAR phase delays caused by the height differences between the current topography and a Digital Elevation Model (DEM). This does not require a pre-event SAR image, so it does not rely on interferometric phase remaining coherent during eruption and emplacement. Synthetic tests predicts that we can estimate lava thickness of as little as �9 m, given a minimum of 5 interferograms with suitably large orbital baseine separations. In the case of continuous motion, such as lava flow subsidence, we invert interferometric phase simultaneously for topographic change and displacement. We demonstrate the method using data from Santiaguito volcano, Guatemala, and measure increases in lava thickness of up to 140 m between 2000 and 2009, largely associated with activity between 2000 and 2005. We find a mean extrusion rate of 0.43 +/- 0.06 m3/s, which lies within the error bounds of the longer term extrusion rate between 1922-2000. The thickest and youngest parts of the flow deposit were shown to be subsiding at an average rate of �-6 cm/yr. This is the first time that flow thickness and subsidence have been measured simultaneously. We expect this method to be suitable for measurment of landslides and other mass flow deposits as well as lava flows.

A rate and state friction law for saline ice

Sea ice friction models are necessary to predict the nature of interactions between sea ice floes. These interactions are of interest on a range of scales, for example, to predict loads on engineering structures in icy waters or to understand the basin-scale motion of sea ice. Many models use Amonton's friction law due to its simplicity. More advanced models allow for hydrodynamic lubrication and refreezing of asperities; however, modeling these processes leads to greatly increased complexity. In this paper we propose, by analogy with rock physics, that a rate- and state-dependent friction law allows us to incorporate memory (and thus the effects of lubrication and bonding) into ice friction models without a great increase in complexity. We support this proposal with experimental data on both the laboratory (∼0.1 m) and ice tank (∼1 m) scale. These experiments show that the effects of static contact under normal load can be incorporated into a friction model. We find the parameters for a first-order rate and state model to be A = 0.310, B = 0.382, and μ0 = 0.872. Such a model then allows us to make predictions about the nature of memory effects in moving ice-ice contacts.

Grouping of 24 apple cultivars on the basis of starch degradation rate and their fruit pattern

The ripening processes of 24 apple cultivars were examined in the United Kingdom National Fruit Collection in 2010. Basically the starch content, and additionally ground colour, water-soluble solids content and flesh firmness were studied during ripening. The degradation of the starch content was evaluated using a 0–10 scale. A starch degradation value of 50% was taken to be the optimum harvest date, with harvest beginning at a value of 40% and finishing at 60%. Depending on the cultivar, this represented a harvest window of 9 to 21 days. Later ripening cultivars matured more slowly, leading to a longer harvesting period, with the exception of cv. Feuillemorte. Pronounced differences were observed among the cultivars on the basis of the starch degradation pattern, allowing them to be divided into four groups. Separate charts were elaborated for each group that are recommended for use in practice.

Quantile forecasts of daily exchange rate returns from forecasts of realized volatility

Quantile forecasts are central to risk management decisions because of the widespread use of Value-at-Risk. A quantile forecast is the product of two factors: the model used to forecast volatility, and the method of computing quantiles from the volatility forecasts. In this paper we calculate and evaluate quantile forecasts of the daily exchange rate returns of five currencies. The forecasting models that have been used in recent analyses of the predictability of daily realized volatility permit a comparison of the predictive power of different measures of intraday variation and intraday returns in forecasting exchange rate variability. The methods of computing quantile forecasts include making distributional assumptions for future daily returns as well as using the empirical distribution of predicted standardized returns with both rolling and recursive samples. Our main findings are that the Heterogenous Autoregressive model provides more accurate volatility and quantile forecasts for currencies which experience shifts in volatility, such as the Canadian dollar, and that the use of the empirical distribution to calculate quantiles can improve forecasts when there are shifts

What will be the risk-free rate and benchmark yield curve following European monetary union?

Using a linear factor model, we study the behaviour of French, Germany, Italian and British sovereign yield curves in the run up to EMU. This allows us to determine which of these yield curves might best approximate a benchmark yield curve post EMU. We find that the best approximation for the risk free yield is the UK three month T-bill yield, followed by the German three month T-bill yield. As no one sovereign yield curve dominates all others, we find that a composite yield curve, consisting of French, Italian and UK bonds at different maturity points along the yield curve should be the benchmark post EMU.

A Double-threshold GARCH Model for the French Franc/Deutschmark exchange rate

This paper combines and generalizes a number of recent time series models of daily exchange rate series by using a SETAR model which also allows the variance equation of a GARCH specification for the error terms to be drawn from more than one regime. An application of the model to the French Franc/Deutschmark exchange rate demonstrates that out-of-sample forecasts for the exchange rate volatility are also improved when the restriction that the data it is drawn from a single regime is removed. This result highlights the importance of considering both types of regime shift (i.e. thresholds in variance as well as in mean) when analysing financial time series.

Bicorrelations and cross-bicorrelations as non-linearity tests and tools for exchange rate forecasting

This paper proposes and implements a new methodology for forecasting time series, based on bicorrelations and cross-bicorrelations. It is shown that the forecasting technique arises as a natural extension of, and as a complement to, existing univariate and multivariate non-linearity tests. The formulations are essentially modified autoregressive or vector autoregressive models respectively, which can be estimated using ordinary least squares. The techniques are applied to a set of high-frequency exchange rate returns, and their out-of-sample forecasting performance is compared to that of other time series models