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Considerable Discrepancies (considerable + discrepancy)

Distribution by Scientific Domains

Chemistry	40%

Selected Abstracts

Sum rules and exact relations for quantal Coulomb systems

CONTRIBUTIONS TO PLASMA PHYSICS, Issue 5-6 2003
V.M. Adamyan
Abstract A complex response function describing a reaction of a multi-particle system to a weak alternating external field is the boundary value of a Nevanlinna class function (i.e. a holomorphic function with non-negative imaginary part in the upper half-plane). Attempts of direct calculations of response functions based on standard approximations of the kinetic theory for real Coulomb condensed systems often result in considerable discrepancies with experiments and computer simulations. At the same time a relatively simple approach using only the exact values of leading asymptotic terms of the response function permits to restrict essentially a subset of Nevanlinna class functions containing this response function, and in this way to obtain sufficient data to explain and predict experimental results. Mathematical details of this approach are demonstrated on an example with the response function being the (external) dynamic electrical conductivity of cold dense hydrogen-like plasmas. In particular, the exact values of the leading terms of asymptotic expansions of the conductivity are calculated. (© 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim) [source]

Obtaining thermochemical data by the extended kinetic method

JOURNAL OF MASS SPECTROMETRY (INCORP BIOLOGICAL MASS SPECTROMETRY), Issue 9 2004
Guy Bouchoux
Abstract A microcanonical analysis of the extended kinetic method is performed using statistical rate calculations based on orbiting transition state theory. The model systems simulate polydentate bases M which exhibit losses of entropy upon protonation of up to 35 kJ mol,1 K,1. It is shown that the correlations using the natural logarithm of the ratio of rate constants vs the proton affinity of the reference bases, at several effective temperatures, lead to correct proton affinity and protonation entropy of the base M of interest. A systematic underestimate of the latter quantity (by 5,15%), mainly due to the use of a linear rather than a polynomial curve fitting procedure, is noted, however. When considering experimental data, more severe underestimates are observed for the protonation entropies of polydentate bases (by 50,90%). The origins of these considerable discrepancies are beyond the limits of the present modeling and remain to be determined. Copyright © 2004 John Wiley & Sons, Ltd. [source]

On the origin of topological differences between experimental and theoretical crystal charge densities

ACTA CRYSTALLOGRAPHICA SECTION A, Issue 4 2000
Anatoliy Volkov
Topological analysis of experimental and theoretical (molecular and crystal) electron densities of p -nitroaniline and p -amino- p,-nitrobiphenyl reveals considerable discrepancies between experiment and theory for the bond critical points properties. Particularly large differences occur for the positive curvature along the bond path (,3). The differences become somewhat smaller when more extended basis sets and correlation effects are introduced in the theoretical calculations. The effect of the crystal matrix on the properties of bond critical points is evaluated for the p -nitroaniline molecule using the 6-21G** and 6-31G** basis sets. The differences between the isolated molecule and the molecule in the crystal are too small to explain the quantitative disagreement between the theoretical and experimental topologies reported in the literature and found in the current study. For most bonds, the observed changes in the properties of the electron density agree well for both basis sets but some discrepancies are found for changes in ,3 for N,H and aromatic C,C bonds. When the theoretical densities are projected into the multipole density functions through refinement of the theoretical structure factors, the topological properties change and differences between theory and experiment are reduced. The main origin of the observed discrepancies is attributed to the nature of the radial functions in the experimental multipole model. [source]

Forecasting daily high ozone concentrations by classification trees

ENVIRONMETRICS, Issue 2 2004
F. Bruno
Abstract This article proposes the use of classification trees (CART) as a suitable technique for forecasting the daily exceedance of ozone standards established by Italian law. A model is formulated for predicting, 1 and 2 days beforehand, the most probable class of the maximum daily urban ozone concentration in the city of Bologna. The standard employed is the so-called ,warning level' (180,,g/m3). Meteorological forecasted variables are considered as predictors. Pollution data show a considerable discrepancy between the dimensions of the two classes of events. The first class includes those days when the observed maximum value exceeds the established standard, while the second class contains those when the observed maximum value does not exceed the said standard. Due to this peculiarity, model selection procedures using cross-validation usually lead to overpruning. We can overcome this drawback by means of techniques which replicate observations, through the modification of their inclusion probabilities in the cross-validation sets. Copyright © 2004 John Wiley & Sons, Ltd. [source]

Thermal Degradation Kinetics of Nylon 66: Experimental Study and Comparison with Model Predictions

MACROMOLECULAR REACTION ENGINEERING, Issue 5 2007
Mark A. Schaffer
Abstract An experimental investigation of nonoxidative thermal degradation kinetics of nylon 66 melt under high temperature (280,300,°C) and low water content (0.02,0.14 wt.-%) conditions is presented. Experimental data for the time evolution of polymer end-group concentrations and degradation-product generation rates were compared with the predictions of the only published kinetic model. The omitted influence of water content is a plausible partial explanation for the considerable discrepancy between model predictions and some data. Several previously unreported or unquantified degradation products were identified and measured. Potential additional reactions to account for these results in future kinetic models are proposed. [source]