H2S ultrafast dissociation probed by energy-selected resonant Auger electron-ion coincidence measurements

We have studied the ultrafast dissociation of the H2S molecule upon S 2p3/2-->6a1 inner-shell excitation by combining high-resolution resonant Auger spectroscopy and energy-selected Auger electron-ion coincidence measurements. Auger final states have been correlated to the different fragmentation pathways (S+, HS+, and H2S+ ions). As an original result, we evidence a three-step mechanism to describe the resonant production of S+: the Auger recombination in the HS* fragment is followed for the A 3Pi and c 1Pi states by the S++H fragmentation mechanism.     

Specific thermoresponsiveness of PMMA-block-PDMAEMA to selected ions and other factors in aqueous solution

Poly(2-(dimethylamino)ethyl methacrylate) (PDMAEMA) is a functional polymer that presents positive charges at low and neutral pHs. Copolymers bearing PDMAEMA blocks usually show a thermal behavior in water marked by a lower critical solution temperature (LCST). This behavior suggests them as interesting “smart” materials for several applications such as water decontamination and many others. In the present work, the LCST of a poly(methyl methacrylate)-block-poly(2-(dimethylamino)ethyl methacrylate) (PMMA-b-PDMAEMA) synthesized by RAFT was measured in several conditions in aqueous solution. It was demonstrated that ionic strength modulates the LCST and this effect depends on the nature of the anion. For instance, weakly hydrated anions such as perchlorate make the LCST lower as the ionic strength gets higher, on the other hand, strongly hydrated ions such as sulfate have not shown a marked effect on LCST. Those results were understood as a consequence of the specific binding of each anion onto the positive-charged PDMAEMA chains, changing the interactions between the chains and water molecules, as well as affecting their pK _a and the ionic interactions. Also, as expected, the LCST is very dependent on pH. The overall results point to the opportunity of modulating very precisely the thermal behavior of PMMA-b-PDMAEMA systems by usual solution conditions such as the type of the anion present.     

Remarkable Nonlinear Properties of a Novel Quinolidone Derivative: Joint Synthesis and Molecular Modeling

A novel 4(1H) quinolinone derivative (QBCP) was synthesized and characterized with single crystal X-ray diffraction. Hirshfeld surfaces (HS) analyses were employed as a complementary tool to evaluate the crystal intermolecular interactions. The molecular global reactivity parameters of QBCP were studied using HOMO and LUMO energies. In addition, the molecular electrostatic potential (MEP) and the UV-Vis absorption and emission spectra were obtained and analyzed. The supermolecule (SM) approach was employed to build a bulk with 474,552 atoms to simulate the crystalline environment polarization effect on the asymmetric unit of the compound. The nonlinear optical properties were investigated using the density functional method (DFT/CAM-B3LYP) with the Pople’s 6-311++G(d,p) basis set. The quantum DFT results of the linear polarizability, the average second-order hyperpolarizability and the third-order nonlinear susceptibility values were computed and analyzed. The results showed that the organic compound (QBCP) has great potential for application as a third-order nonlinear optical material.     

Études sur les matières végétales volatiles. CCII. Synthèse d'aldéhyde phénylacétique à partir du styrolène

On treatment of styrolene between 30 and 40°C with performic acid, phenylglycol monoformate is produced.     

Etudes sur les matières végétales volatiles CXCVIII. Contribution à la connaissance des farnésènes

The dehydration of farnesols or nerolidols is similar to that of geraniol and nerol or linalool. It yields a mixture of hydrocarbons including trans-β-farnesene, two allofarnesenes, α-curcumene, α-, β- and γ-bisabolenes, and triterpenes. The triterpenes result from dienisation of β-farnesenes or α-farnesenes with β-farnesenes, or dimerization of allofarnesenes.     

Transpositions de doubles liaisons de terpènes bicycliques catalysées par des bases

The displacements of double bonds and dehydrogenation by basic catalysts are examined by analogy with the preceding studies on p-menthenes and p-menthadienes [1] with bicyclic terpenes: α- and β-pinenes, sabinene and 3-carene.     

Core localization and sigma* delocalization in the O 1s core-excited sulfur dioxide molecule

Electron-ion-ion coincidence measurements of sulfur dioxide at discrete resonances near the O 1s ionization edge are reported. The spectra are analyzed using a model based upon molecular symmetry and on the geometry of the molecule. We find clear evidence for molecular alignment that can be ascribed to symmetry properties of the ground and core-excited states. Configuration interaction (CI) calculations indicate geometry changes in accord with the measured spectra. For the SO(2) molecule, however, we find that the localized core hole does not produce measurable evidence for valence localization, since the transition dipole moment is not parallel to a breaking sigma* O-S bond, in contrast to the case of ozone. The dissociation behavior based upon the CI calculations using symmetry-broken orbitals while fixing a localized core-hole site is found to be nearly equivalent to that using symmetry-adapted orbitals. This implies that the core-localization effect is not strong enough to localize the sigma* valence orbital.     

Size dependent fragmentation of argon clusters in the soft x-ray ionization regime

Photofragmentation of argon clusters of average size ranging from 10 up to 1000 atoms is studied using soft x-ray radiation below the 2p threshold and multicoincidence mass spectroscopy technique. For small clusters (=10), ionization induces fast fragmentation with neutral emission imparting a large amount of energy. While the primary dissociation takes place on a picosecond time scale, the fragments undergo slow degradation in the spectrometer on a microsecond time scale. For larger clusters ( >or=100) we believe that we observe the fragmentation pattern of multiply charged species on a time-scale which lasts a few hundred nanoseconds. The reason for these slower processes is the large number of neutral atoms which act as an efficient cooling bath where the excess energy ("heat") dissipates among all degrees of freedom. Further degradation of the photoionic cluster in spectrometer then takes place on the microsecond time scale, similar to small clusters.     

Generating random graphs in biased Maker‐Breaker games

We present a general approach connecting biased Maker‐Breaker games and problems about local resilience in random graphs. We utilize this approach to prove new results and also to derive some known results about biased Maker‐Breaker games. In particular, we show that for , Maker can build a pancyclic graph (that is, a graph that contains cycles of every possible length) while playing a game on . As another application, we show that for , playing a game on , Maker can build a graph which contains copies of all spanning trees having maximum degree with a bare path of linear length (a bare path in a tree T is a path with all interior vertices of degree exactly two in T). © 2015 Wiley Periodicals, Inc. Random Struct. Alg., 47, 615–634, 2015