Topological properties of the electronic density of CO-MgF2 and OC-MgF2 adducts

By means of Bader's approach on topological properties of the electronic density, the major stability of the O-bonded adduct over the C-bonded one between MgF₂ and CO is reinforced.     

Some electronic correlation effects in the topological analysis of the Laplacian of the electronic charge density in C-n-butonium cations

In this work, we present a topological study of the Laplacian of the electronic density using a 6-311++G basis set, at Hartree-Fock (HF) and second-order M?ller-Plesset (MP2) (full-electron and frozen-core) levels of theory, for the carbocations 2-C-n-butonium generated upon the insertion of a proton into the secondary C-C bond during the protonation of n-butane. The charge concentration, CC, critical points of the Laplacian distribution at each valence shell, VS, of carbon atoms, and the charge concentration closer to hydrogen atoms are studied. Also, the bonding critical points of the electronic density are analyzed. We analyze some effects that Coulomb correlation has on topological features of the electronic distribution. It is shown that they are mainly reflected in a decreasing of the charge concentrations at the VS and in a contraction of the VS to the nuclei. They are more pronounced over C-C bonds than in C-H bonds. The sensitivity of some parameters derived from this topological analysis to the correlation effect of core electrons and subtle effects related to hyperconjugative interactions are shown. Some consequences of different schemes (double and triple split-valence basis set with diffuse and polarization functions) in the definition of subtle VS charge concentrations at 3c-2e bond paths are presented. It is also demonstrated here how the facts that allow us to understand the MP2 stability order found in the carbocationic species 2-C-n-butonium > 1-C-n-butonium > 2-H-n-butonium > 1-H-n-butonium are similarly depicted at correlated and uncorrelated levels of calculation.     

Influence of functional nanoparticles on the photostability of polymer materials: Recent progress and further applications

The photochemical behaviour of polymer–nanoparticles/nanocomposites has been studied depending on the geometry of the nanofiller and an overview of the studies reported in the last decade is tentatively given. Depending on their functionality, nanoparticles can impact the durability of the nanocomposite materials under light irradiation. The behaviour to UV-light exposure in presence of oxygen of various types of nanocomposites with clays, LDH and carbon nanotubes has been investigated and recent progress on the influence of functional nanoparticles on the polymer photodegradation is reported. The influence of photocatalytic (ZnO and TiO₂) nanoparticles and phosphors on the photooxidation of the polymeric matrix and the durability of the material properties are characterized. From a general point of view, the stabilization strategy of polymer nanocomposites must be adapted depending on the nanofiller.     

Semiempirical SCF/CI interpretation of the origin of the catalytic activity of transition metal-macrocycle complexes

Semiempirical self-consistent field (SCF) and configuration interaction (CI) calculations of the intermediate neglect of differential overlap (INDO) type are applied to the analysis of the electronic transitions of the hexaazacyclophane base and its Ni and Cu complexes. The ground states (¹A_g for the ligand and Ni complex, ²B_1g for the Cu complex) are planar structures of D₂h symmetry. The low-energy region of the UV-visible spectra, whose analysis may help to recognize the catalytic active sites of the complexes is associated with d → d transitions in the Ni complex, and M → L charge transfer in the Cu complex.     

Unimolecular decomposition of CF3OF-calculation by reduced Kassel integral in factorized form

The fall-off curves were calculated for the unimolecular decomposition of the trifluoromethyl hypofluorite at 475.8, 496.9 and 507.3 K by means of the Reduced Kassel Integral in Factorized Form.

---

475,8,496,9 507,3 .

     

Theoretical calculation of the singlet-triplet electronic transition and photochemical reactivity in carbonyl fluoride,trifluoroacetyl fluoride and perfluoromethyl perfluoroacetate

Molecular properties following electronic excitation were studied and calculations were performed for the singlet-triplet electronic transitions of carbonyl fluoride, perfluoroacetyl fluoride and perfluoromethyl perfluoroacetate by means of the CNDO/S-CI method. Various approximations were used to evaluate the core Hamiltonian matrix elements.     

Experimental evidence of energy pumping in acousticsMise en évidence expérimentale de pompage énergétique en acoustique

This Note presents an experimental vibro-acoustic set-up that aims to reproduce the energy pumping phenomenon between an acoustic medium and an essentially nonlinear oscillator. It shows a one-way irreversible transfer of energy between the first acoustic mode in a tube and a thin visco-elastic membrane. To cite this article: B. Cochelin et al., C. R. Mecanique 334 (2006).     

Study of the structural and electronic properties of valproic acid and new derivatives used as anticonvulsant agents

The conformational and electronic characteristics of the polar O(9)═C(8)-X(10) moiety in the anticonvulsant valproic acid (Vpa) drug and some of their amides and ester derivatives are analyzed at the B3LYP level using the 6-31+G(d,p) and 6-311++G(d,p) 6d,10f basis sets. Exploring the delocalization of the electron density of the O(9)═C(8)-X(10) moiety by means of ELF, NBO, and AIM calculations, we found that the bending away from coplanarity of the atoms in O(9)═C(8)-X(10) is accompanied by a three-dimensional arrangement of donor and acceptor proton units closing nearly planar pseudorings of four, five, and six members arising from stabilizing interactions around the O(9)═C(8)-X(10) backbone. From the structure-property relationship analysis, we explain the origin of the change in the structural parameters and atomic charges in the polar moiety.     

Response of a Thin Cylindrical Shell Excited by a Turbulent Internal Flow

This paper presents results obtained within the scope of a collaboration between the “Laboratoire de Mécanique et d'Acoustique” (Marseille, France), the “Laboratoire de Mécanique des Fluides et d'Acoustique” of the Ecole Centrale (Lyon, France) and the “Laboratoire de Vibrations et d'Acoustique” of the Institut National des Sciences Appliquées (Lyon, France). The main aspect of this collaboration is to establish a comparison between a measured and a model vibro-acoustics response of a thin cylindrical pipe excited by a turbulent internal flow. After a brief review of the literature, a model of the response of the shell, based on a matched asymptotic expansion, is given. Some numerical results are also given. The spectral density of the acceleration of the shell is compared with experimental results. This revised version was published online in July 2006 with corrections to the Cover Date.