Cyclobutadiene automerization and rotation of ethylene: Energetics of the barriers by using Spin-polarized wave functions

Spin-projected spin polarized Møller–Plesset and spin polarized coupled clusters calculations have been made to estimate the cyclobutadiene automerization, the ethylene torsion barriers in their ground state, and the gap between the singlet and triplet states of ethylene. The results have been obtained optimizing the geometries at MP4 and/or CCSD levels, by an extensive Gaussian basis set. A comparative analysis with more complex calculations, up to MP5 and CCSDTQP, together with others from the literature, have also been made, showing the efficacy of using spin-polarized wave functions as a reference wave function for Møller–Plesset and coupled clusters calculations, in such problems.

An adaptive algorithm for clustering cumulative probability distribution functions using the Kolmogorov–Smirnov two-sample test

This paper proposes an adaptive algorithm for clustering cumulative probability distribution functions (c.p.d.f.) of a continuous random variable, observed in different populations, into the minimum homogeneous clusters, making no parametric assumptions about the c.p.d.f.’s. The distance function for clustering c.p.d.f.’s that is proposed is based on the Kolmogorov–Smirnov two sample statistic. This test is able to detect differences in position, dispersion or shape of the c.p.d.f.’s. In our context, this statistic allows us to cluster the recorded data with a homogeneity criterion based on the whole distribution of each data set, and to decide whether it is necessary to add more clusters or not. In this sense, the proposed algorithm is adaptive as it automatically increases the number of clusters only as necessary; therefore, there is no need to fix in advance the number of clusters. The output of the algorithm are the common c.p.d.f. of all observed data in the cluster (the centroid) and, for each cluster, the Kolmogorov–Smirnov statistic between the centroid and the most distant c.p.d.f. The proposed algorithm has been used for a large data set of solar global irradiation spectra distributions. The results obtained enable to reduce all the information of more than 270,000 c.p.d.f.’s in only 6 different clusters that correspond to 6 different c.p.d.f.’s.

On the Result of Invariance of the Closure Set of the Real Projections of the Zeros of an Important Class of Exponential Polynomials

In this paper we provide the proof of a practical point-wise characterization of the set RP defined by the closure set of the real projections of the zeros of an exponential polynomial P(z) = Σn j=1 cjewjz with real frequencies wj linearly independent over the rationals. As a consequence, we give a complete description of the set RP and prove its invariance with respect to the moduli of the c′ js, which allows us to determine exactly the gaps of RP and the extremes of the critical interval of P(z) by solving inequations with positive real numbers. Finally, we analyse the converse of this result of invariance.