Energetics of midvelocity emissions in peripheral heavy ion collisions at Fermi energies

Peripheral and semiperipheral collisions have been studied in the system 93Nb+93Nb at 38A MeV. The evaporative and midvelocity components of the light charged particle and intermediate mass fragment emissions have been carefully disentangled. In this way it was possible to obtain the average amount not only of charge and mass, but also of energy, pertaining to the midvelocity emission, as a function of an impact parameter estimator. This emission has a very important role in the overall balance of the reaction, as it accounts for a large fraction of the emitted mass and for more than half of the dissipated energy. As such, it may give precious clues on the microscopic mechanism of energy transport from the interaction zone toward the target and projectile remnants.     

Dimerization and polymerization of isoprene at high pressures

The high-pressure reactivity of isoprene has been studied at room temperature up to 2.6 GPa by using the diamond anvil cell technique in combination with Fourier transform infrared spectroscopy. Both dimerization and polymerization reactions take place above 1.1 GPa. At this pressure, the two processes are well separated in time, the dimerization being the only one occurring in the first 150 h. Both processes simultaneously occur as the pressure increases. The reaction product is composed of a volatile fraction, identified as sylvestrene, and a transparent rubberlike solid formed by cis-1,4- and 3,4-polyisoprene. The activation volume of the dimerization reaction has been obtained from the kinetic data. The photoinduced reaction, studied at room temperature for two different pressures, takes place through a two-photon absorption process, and the threshold pressure is lowered to 0.5 GPa. At this pressure, both the dimerization and polymerization processes occur, but the dimerization is not as selective as in the purely pressure-induced reaction. 4-Ethenyl-2,4-dimethylcyclohexene is obtained in addition to sylvestrene. By increasing the pressure, the photoinduced reaction becomes more selective, and the monomer is quantitatively transformed into the same polymer obtained in the purely pressure-induced reaction.     

Development of cation/anion "interaction" scales for ionic liquids through ESI-MS measurements

Electrospray ionization mass spectrometry applied to ionic liquids allowed the study of loosely bonded supramolecules, originating from these organic salts. Based on the observation that ionic liquids formed cationic [C(q+1)X(q)](+) and anionic [C(q)X(q+1)](-) supramolecular aggregates, we have investigated mixed networks, formed by different cations coordinated to a selected anion or by different anions bonded to a given cation, i.e., [C1...X...C2](+) and [X1...C...X2](-), with the aim to build a scale of the cation-anion interaction strength. The qualitative order of intrinsic bond strength to Br- was found to be the following: [emim](+) > [bmim](+) > [mor1,2](+) > [hmim]+ > [omim](+) > [mor1,4](+) > [bupy](+) > [bpyrr](+) > [picol](+) > [bm(2)im](+) > [TBA](+). Similarly, the interaction energies to 1-butyl-3-methylimidazolium (bmim) species envisaged two classes of anions: species tightly coordinated to the cationic moiety that include CF3COO(-), Br(-), N(CN)2(-), and BF4(-) and anions loosely interacting with the alkylimidazolium species such as OTf(-), PF6(-), and Tf2N(-).     

Isolation of Elusive Phosphinidene-Chlorotetrylenes: The Heavier Cyanogen Chloride Analogues

The elusive phosphinidene-chlorotetrylenes, [PGeCl] and [PSiCl] have been stabilized by the hetero-bileptic cyclic alkyl(amino) carbene (cAAC), N-heterocyclic carbene (NHC) ligands, and isolated in the solid state at room temperature as the first neutral monomeric species of this class with the general formulae (L)P-ECl(L′) (E=Ge, 3 a – 3 c ; E=Si, 6 ; L=cAAC; L′=NHC). Compounds 3 a – 3 c have been synthesized by the reaction of cAAC-supported potassium phosphinidenides [cAAC=PK(THF)_x]_n ( 1 a – 1 c ) with the adduct NHC:→GeCl₂ ( 2 ). Similarly, compound 6 has been synthesized via reaction of 1 a with NHC:→SiCl₂ adduct ( 4 ). Compounds 3 a – 3 c , and 6 have been structurally characterized by single-crystal X-ray diffraction, NMR spectroscopy and mass spectrometric analysis. DFT calculations revealed that the heteroatom P in 3 bears two lone pairs; the non-bonding pair with 67.8 % of s- and 32 % of p character, whereas the other lone pair is involved in π backdonation to the C_cAAC-N π* of cAAC. The Ge atom in 3 contains a lone pair with 80 % of s character, and slightly involved in the π backdonation to C_NHC. EDA-NOCV analyses showed that two charged doublet fragments {(cAAC)(NHC)}⁺, and {PGeCl}⁻ prefer to form one covalent electron-sharing σ bond, one dative σ bond, one dative π bond, and a charge polarized weak π bond. The covalent electron-sharing σ bond contributes to the major stabilization energy to the total orbital interaction energy of 3 , enabling the first successful isolations of this class of compounds ( 3 , 6 ) in the laboratory.     

Computing the Karcher mean of symmetric positive definite matrices

We present and analyze an iterative method for approximating the Karcher mean of a set of $n\times n$ positive definite matrices $A_i$, $i=1\text{,}\dots \text{,}k$, defined as the unique positive definite solution of the matrix equation ${\sum }_{i=1}^k\log (A_i^{-1}X)=0$.     

de Sitter spacetime: effects of metric perturbations on geodesic motion

Gravitational perturbations of the de Sitter spacetime are investigated using the Regge–Wheeler formalism. The set of perturbation equations is reduced to a single second order differential equation of the Heun-type for both electric and magnetic multipoles. The solution so obtained is used to study the deviation from an initially radial geodesic due to the perturbation. The spectral properties of the perturbed metric are also analyzed. Finally, gauge- and tetrad-invariant first-order massless perturbations of any spin are explored following the approach of Teukolsky. The existence of closed-form, i.e. Liouvillian, solutions to the radial part of the Teukolsky master equation is discussed.     

A note on computing matrix geometric means

A new definition is introduced for the matrix geometric mean of a set of k positive definite n×n matrices together with an iterative method for its computation. The iterative method is locally convergent with cubic convergence and requires O(n ³ k ²) arithmetic operations per step whereas the methods based on the symmetrization technique of Ando et al. (Linear Algebra Appl 385:305?C334, 2004) have complexity O(n ³ k!2 ^k ). The new mean is obtained from the properties of the centroid of a triangle rephrased in terms of geodesics in a suitable Riemannian geometry on the set of positive definite matrices. It satisfies most part of the ten properties stated by Ando, Li and Mathias; a counterexample shows that monotonicity is not fulfilled.     

Ligand development in the Ni-catalyzed hydrocyanation of alkenes

The addition of HCN to alkenes is a very useful reaction for the synthesis of functional organic substrates. Industrially the nickel-catalyzed hydrocyanation has gained considerable importance mainly because of the production of adiponitrile in the DuPont process. In this process the hydrocyanation of butadiene is carried out using aryl phosphite-modified nickel catalyst. Since the performance of organo-transition metal complexes is largely determined by the ligand environment of the metal, fundamental understanding and ligand development is of pivotal importance for any progress. This feature article gives an account of the development and application of different mono- and bidentate phosphorus-based ligands in the Ni-catalyzed hydrocyanation reaction of alkenes. Special attention will be paid to the development of insight and understanding of the ligand structural and electronic properties towards the improvement of the catalyst performance in terms of stability, activity, and selectivity.     

Measurement of Absolute Fluorescence Quantum Yield of Basic Fuchsin Solution Using a Dual-Beam Thermal Lens Technique

The dual beam thermal lens technique is an effective method for the measurement of fluorescence quantum yield of dye solutions. The concentration-dependent quantum yield of a novel dye of triaminotriphenylmethane family in ethanol is studied using this technique. The absolute fluorescence quantum yield is measured and is observed that the reduction in the quantum yield is due to the non-radiative relaxation of the absorbed energy.     

The cyclic reduction algorithm: from Poisson equation to stochastic processes and beyond

Cyclic reduction is an algorithm invented by G. H. Golub and R. W. Hockney in the mid 1960s for solving linear systems related to the finite differences discretization of the Poisson equation over a rectangle. Among the algorithms of Gene Golub, it is one of the most versatile and powerful ever created. Recently, it has been applied to solve different problems from different applicative areas. In this paper we survey the main features of cyclic reduction, relate it to properties of analytic functions, recall its extension to solving more general finite and infinite linear systems, and different kinds of nonlinear matrix equations, including algebraic Riccati equations, with applications to Markov chains, queueing models and transport theory. Some new results concerning the convergence properties of cyclic reduction and its applicability are proved under very weak assumptions. New formulae for overcoming breakdown are provided.