95 resultados para MULTIVARIATE DISTRIBUTIONS
Resumo:
Isotope yield distributions in the multifragmentation regime were studied with high-quality isotope identification, focusing on the intermediate mass fragments (IMFs) produced in semiviolent collisions. The yields were analyzed within the framework of a modified Fisher model. Using the ratio of the mass-dependent symmetry energy coefficient relative to the temperature, a(sym)/T, extracted in previous work and that of the pairing term, a(p)/T, extracted from this work, and assuming that both reflect secondary decay processes, the experimentally observed isotope yields were corrected for these effects. For a given I = N - Z value, the corrected yields of isotopes relative to the yield of C-12 show a power law distribution Y (N, Z)/Y(C-12) similar to A(-tau) in the mass range 1 <= A <= 30, and the distributions are almost identical for the different reactions studied. The observed power law distributions change systematically when I of the isotopes changes and the extracted tau value decreases from 3.9 to 1.0 as I increases from -1 to 3. These observations are well reproduced by a simple deexcitation model, with which the power law distribution of the primary isotopes is determined to be tau(prim) = 2.4 +/- 0.2, suggesting that the disassembling system at the time of the fragment formation is indeed at, or very near, the critical point.
Resumo:
The angular momentum polarization and rotational state distributions of the H-2 and HCl products from the H + HCl reaction are calculated at a relative translational energy of 1.6 eV by using quasiclassical trajectories on two potential energy surfaces, one from G3 surface [T.C. Allison et al., J. Phys. Chem. 100 (1996) 13575], and the other from BW2 surface [W. Bian, H.-J. Werner, J. Chem. Phys. 112 (2000) 220]. Product rotational distributions obtained on the G3 potential energy surface (PES) are much closer to the experimental results (P.M. Aker et al., J. Chem. Phys. 90 (1989) 4795; J. Chem. Phys. 90 (1989) 4809) than the distributions calculated on the BW2 PES. The distributions of P(phi(r)) for the H-2 and HCl products obtained on the G3 PES are similar, whereas the rotational alignment effect of the H-2 product is stronger than that of the HCl product. In contrast to the polarization distributions obtained on the G3 PES, the rotational alignment effect of the two products calculated on the BW2 PES is similar. However, the abstraction reaction is dominated by out-of-plane mechanisms, while the exchange reaction is dominated by in-plane mechanisms. The significant difference of the product rotational polarization obtained on the G3 and BW2 PESs implies that the studies of the dynamical stereochemistry can provide a sensitive test for the accuracy of the PES. (C) 2002 Elsevier Science B.V. All rights reserved.
Resumo:
The optimization of the organic modifier concentration in micellar electrokinetic capillary chromatography (MECC) has been achieved by a uniform design and iterative optimization method, which has been developed for the optimization of composition of the mobile phase in high performance liquid chromatography. According to the proposed method, the uniform design technique has been applied to design the starting experiments, which can reduce the number of experiments compared with traditional simultaneous methods, such as the orthano design. The hierarchical chromatographic response function has been modified to evaluate the separation quality of a chromatogram in MECC. An iterative procedure has been adopted to search the optimal concentration of organic modifiers for improving the accuracy of retention predicted and the quality of the chromatogram. Validity of the optimization method has been proved by the separation of 31 aromatic compounds in MECC. (C) 2000 John Wiley & Sons, Inc.
Resumo:
Changes in statistics (mean, sorting, and skewness) describing grain-size distributions have long been used to speculate on the direction of sediment transport. We present a simple model whereby the distributions of sediment in transport are related to their source by a sediment transfer function which defines the relative probability that a grain within each particular class interval will be eroded and transported. A variety of empirically derived transfer functions exhibit negatively skewed distributions (on a phi scale). Thus, when a sediment is being eroded, the probability of any grain going into transport increases with diminishing grain size throughout more than half of its size range. This causes the sediment in transport to be finer and more negatively skewed than its source, whereas the remaining sediment (a lag) must become relatively coarser and more positively skewed. Flume experiments show that the distributions of transfer functions change from having a highly negative skewness to being nearly symmetrical (although still negatively skewed) as the energy of the transporting process increases. We call the two extremes low-energy and high-energy transfer functions , respectively. In an expanded sediment-transport model, successive deposits in the direction of transport are related by a combination of two transfer functions. If energy is decreasing and the transfer functions have low-energy distributions, successive deposits will become finer and more negatively skewed. If, however, energy is decreasing, but the initial transfer function has a high-energy distribution, successive deposits will become coarser and more positively skewed. The variance of the distributions of lags, sediment in transport, and successive deposits in the down-current direction must eventually decrease (i.e., the sediments will become better sorted). We demonstrate that it is possible for variance first to increase, but suggest that, in reality, an increasing variance in the direction of transport will seldom be observed, particularly when grain-size distributions are described in phi units. This model describing changes in sediment distributions was tested in a variety of environments where the transport direction was known. The results indicate that the model has real-world validity and can provide a method to predict the directions of sediment transport
Resumo:
We developed a coarse-grained yet microscopic detailed model to study the statistical fluctuations of single-molecule protein conformational dynamics of adenylate kinase. We explored the underlying conformational energy landscape and found that the system has two basins of attractions, open and closed conformations connected by two separate pathways. The kinetics is found to be nonexponential, consistent with single-molecule conformational dynamics experiments. Furthermore, we found that the statistical distribution of the kinetic times for the conformational transition has a long power law tail, reflecting the exponential density of state of the underlying landscape. We also studied the joint distribution of the two pathways and found memory effects.
Resumo:
Two soluble high-performance polyimides, poly(BCPOBDA/DMMDA) and poly(ODPA/DMMDA), in CHCl3 at 25 degrees C have been studied using laser light scattering. We found that the z-average radius of gyration ([R(g)]) can be scaled to the weight-average molecular weight (M(w)) as [R(g)] (nm) = 4.95 x 10(-2)M(w)(0.52) and [R(g)] (nm) = 1.25 x 10(-2)M(w)(0.66) respectively for poly(BCPOBDA/DMMDA) and poly(ODPA/DMMDA), indicating that poly(ODPA/DMMDA) in CHCl3 at 25 degrees C has a more extended chain conformation than poly(BCPOBDA/DMMDA). Using the wormlike chain model approach, we found that the Flory characteristic ratios (C*) of poly(BCPOBDA/DMMDA) and poly(ODPA/DMMDA) are similar to 20 and similar to 31, respectively, indicating that both of them have a slightly extended chain conformation in comparison with typical flexible polymer chains, such as polystyrene, whose C-infinity is similar to 10. A combination of the weight-average molar mass (M(w)) with the translational diffusion coefficient distributions (G(D)) has led to D (cm(2)/s) = 3.53 x 10(-4)M(-0.579) and D (cm(2)/s) = 4.30 x 10(-4)M(-0.613) respectively for two soluble high-performance polyimides, poly(BCPOBDA/DMMDA) and poly(ODPA/DMMTA), in CHCl3 at 25 degrees C. Using these two calibrations, we have successfully characterized the molar mass distributions of the two polyimides from their corresponding G(D)s. The exponents of these two calibrations further confirm that both of the polyimides have a slightly extended coil chain conformation in CHCl3. The chain flexibility difference between these two polyimides has also been discussed.
Resumo:
Multivariate classification methods were used to evaluate data on the concentrations of eight metals in human senile lenses measured by atomic absorption spectrometry. Principal components analysis and hierarchical clustering separated senile cataract lenses, nuclei from cataract lenses, and normal lenses into three classes on the basis of the eight elements. Stepwise discriminant analysis was applied to give discriminant functions with five selected variables. Results provided by the linear learning machine method were also satisfactory; the k-nearest neighbour method was less useful.