Kinetics of the thermal decomposition of bis(trifluoromethyl) peroxydicarbonate,CF3OC(O)OOC(O)OCF3

Thermal decomposition of bis(trifluoromethyl) peroxydicarbonate has been studied. The mechanism of decomposition is a simple bond fission, homogeneous first‐order process when the reaction is carried out in the presence of inert gases such as N₂ or CO. An activation energy of 28.5 kcal mol^?1 was determined for the temperature range of 50–90°C. Decomposition is accelerated by nitric oxide because of a chemical attack on the peroxide forming substances different from those formed with N₂ or CO. An interpretation on the influence of the substituents in different peroxides on the O? O bond is given. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 35: 15–19, 2003     

Determining radii of meromorphy via orthogonal polynomials on the unit circle

Using a convergence theorem for Fourier–Padé approximants constructed from orthogonal polynomials on the unit circle, we prove an analogue of Hadamard's theorem for determining the radius of m-meromorphy of a function analytic on the unit disk and apply this to the location of poles of the reciprocal of Szeg functions.     

Asymptotic properties of computationally efficient alternative estimators for a class of multivariate normal models

Parameters of Gaussian multivariate models are often estimated using the maximum likelihood approach. In spite of its merits, this methodology is not practical when the sample size is very large, as, for example, in the case of massive georeferenced data sets. In this paper, we study the asymptotic properties of the estimators that minimize three alternatives to the likelihood function, designed to increase the computational efficiency. This is achieved by applying the information sandwich technique to expansions of the pseudo-likelihood functions as quadratic forms of independent normal random variables. Theoretical calculations are given for a first-order autoregressive time series and then extended to a two-dimensional autoregressive process on a lattice. We compare the efficiency of the three estimators to that of the maximum likelihood estimator as well as among themselves, using numerical calculations of the theoretical results and simulations.     

Dihalodimethyltin(IV) complexes of 2‐(pyrazol‐1‐ylmethyl)pyridine

Reaction of dichloro‐ and dibromodimethyltin(IV) with 2‐(pyrazol‐1‐ylmethyl)pyridine (PMP) afforded [SnMe₂Cl₂(PMP)] and [SnMe₂Br₂(PMP)] respectively. The new complexes were characterized by elemental analysis and mass spectrometry and by IR, Raman and NMR (¹H, ¹³C) spectroscopies. Structural studies by X‐ray diffraction techniques show that the compounds consist of discrete units with the tin atom octahedrally coordinated to the carbon atoms of the two methyl groups in a trans disposition (Sn? C = 2.097(5), 2.120(5) Å and 2.110(6), 2.121(6) Å in the chloro and in the bromo compounds respectively), two cis halogen atoms (Sn? Cl = 2.4908(16), 2.5447(17) Å; Sn? Br = 2.6875(11), 2.7464(9) Å) and the two donor atoms of the ligand (Sn? N = 2.407(4), 2.471(4) Å and 2.360(5), 2.455(5) Å). In both cases, the Sn? N(pyridine) bond length is markedly longer than the Sn? N(pyrazole) distance. Copyright © 2003 John Wiley & Sons, Ltd.     

Speed of adaptation in structured populations

Adaptation of populations takes place with the occurrence and subsequent fixation of mutations that confer some selective advantage to the individuals which acquire it. For this reason, the study of the process of fixation of advantageous mutations has a long history in the population genetics literature. Particularly, the previous investigations aimed to find out the main evolutionary forces affecting the strength of natural selection in the populations. In the current work, we investigate the dynamics of fixation of beneficial mutations in a subdivided population. The subpopulations (demes) can exchange migrants among their neighbors, in a migration network which is assumed to have either a random graph or a scale-free topology. We have observed that the migration rate drastically affects the dynamics of mutation fixation, despite of the fact that the probability of fixation is invariant on the migration rate, accordingly to Maruyama's conjecture. In addition, we have noticed a topological dependence of the adaptive evolution of the population when clonal interference becomes effective.     

Diagramme polythermique du systeme ternaire H2O—Al(NO3)3—Mg(NO3)2

The solid—liquid equilibria of the ternary system H₂O—Al(NO₃)₃—Mg(NO₃)₂ were studied at –30, –20, –10 and 0°C by using a synthetic method which allows to detemine all the characteristic points of isothermal sections. The stable solid phases which appear are respectively: ice, Al(NO₃)₃·9H₂O, Mg(NO₃)₂·9H₂O and Mg(NO₃)₂·6H₂O. Neither double salts nor mixed crystals are observed in the temperature and composition field studied. Polytherm diagram layout show two invariant transformations correspond with an eutectic point and a peritectic point.This revised version was published online in November 2005 with corrections to the Cover Date.     

Multipole-Bound Molecular Negative Ions

 Within the framework of a simple electrostatic model, as compared to recent experimental results, we here discuss the stability of very weakly bound molecular negative ions. In contrast with the case of conventional valence anions, the excess electron is then located in a very diffuse orbital and is mainly bound by electrostatic dipolar, quadrupolar, and polarization forces, at large distances from the neutral molecular core. By fitting a single repulsion parameter of the model to the available experimental data, it is possible to make quantitative predictions of the excess-electron binding energies in these species. Critical values of the dipole moment, quadrupole moment or polarizability required for the observation of stable multipole-bound negative ions are predicted and compared to available experimental data and ab initio calculations. Received October 24, 2001; accepted for publication November 16, 2001     

[VS_4Cu_6(Py)_8I_3]的合成和晶体结构

在(NH4)3VS4/CuI/Py反应体系中合成了新化合物 [VS4Cu6(Py)8I3]并测定其晶体结构。该化合物(C40H40N8Cu6I3S4V)属正交晶系, 空间群为Fdd2, 晶胞参数为: a = 29.924(6), b = 13.475(3), c = 25.853(5) , V = 10425(4) ?, Dc = 2.006 g/cm3, Mr = 1573.92, Z = 8, (MoK) = 4.546 mm-1, F(000) = 6048。结构由直接法解出, 用全矩阵最小二乘法修正, 最终偏离因子R = 0.023, wR = 0.069。簇合物分子是由6个带端基配体的Cu沿着四面体单元VS4的6条SS边配位而成, 6个Cu排列成了1个八面体, V基本位于八面体的中心, 整个分子具有C2对称性。