Application of the “helium excitation standard” procedure to some hydrocarbon Hβ absolute emission cross section measurements

Absolute emission cross sections for H_β radiation are presented. The H_β emission is obtained by dissociative electron excitation of propane, propylene, n-butane and 1-butene under binary collision conditions. Optical excitation functions measured for these transitions are normalized by the “helium excitation standard” procedure, using the 4 ¹S-2 ¹P transition in He as a standard at an electron impact energy of 100 eV. The results obtained are determined with an accuracy of ± 15%. The investigated energy interval is 50–500 eV. The experimental results show that the emission cross sections for H_β radiation are not independent of the number of atoms in the parent molecule.     

The reaction of alkoxides with dicobalt octacarbonyl: Trapping of the Co(I) intermediate in the disproportionation (“base reaction”) with a hardLewis base

Dicobalt octacarbonyl reacts with alcoholates (RO^–) yielding alkoxycarbonylcobalt tetracarbonyls,ROC(O)Co(CO)₄.

---

Reaktion von Alkoxiden mit Dicobaltoctacarbonyl: Abfangen des Co(I) Zwischenproduktes in der Disproportionierung (Basen-Reaktion) mit einer hartenLewis Base (Kurze Mitteilung)

Zusammenfassung Dicobaltoctacarbonyl reagiert mit Alkoxiden (RO^–) zu Alkoxycarbonylcobalt tetracarbonylen,ROC(O)Co(CO)₄.

     

On the Partially Ordered Semigroup Generated by the Class Operators I,R,H,S,P

Let I, H, S, P be the usual class operators on universal algebras. For a class K of universal algebras of the same type, let R({K}) be the class of all algebras isomorphic to a retract of a member of K and let R denote the corresponding class operator. In this paper the semigroup generated by class operators I, R, H, S, P and the corresponding partially ordered set are described. Also the standard semigroups of the above operators are determined for some varieties.     

Desorption electrospray ionization–mass spectrometric analysis of low vapor pressure chemical particulates collected from a surface

The collection of a low vapor pressure chemical simulant triethyl phosphate sorbed onto silica gel (TEP/SG) from a surface with subsequent analysis of the TEP/SG particulates using desorption electrospray ionization–mass spectrometry (DESI–MS) is described. Collection of TEP/SG particulates on a surface was accomplished using a sticky screen sampler composed of a stainless steel screen coated with partially polymerized polydimethylsiloxane (PDMS). DESI–MS analysis of TEP/SG particulates containing different percentages of TEP sorbed onto silica gel enabled the generation of response curves for the TEP ions m/z 155 and m/z 127. Using the response curves the calculation of the mass of TEP in a 25 wt% sample of TEP/SG was calculated, results show that the calculated mass of TEP was 14% different from the actual mass of TEP in the sample using the m/z 127 TEP ion response curve. Detection limits for the TEP vapor and TEP/SG particulates were calculated to be 4 μg and 6 particles, respectively.     

On the growth of Betti numbers of locally symmetric spaces

We announce new results concerning the asymptotic behavior of the Betti numbers of higher rank locally symmetric spaces as their volumes tend to infinity. Our main theorem is a uniform version of the Lück Approximation Theorem (Lück, 1994 [10]) which is much stronger than the linear upper bounds on Betti numbers given by Gromov in Ballmann et al. (1985) [3].The basic idea is to adapt the theory of local convergence, originally introduced for sequences of graphs of bounded degree by Benjamini and Schramm, to sequences of Riemannian manifolds. Using rigidity theory we are able to show that when the volume tends to infinity, the manifolds locally converge to the universal cover in a sufficiently strong manner that allows us to derive the convergence of the normalized Betti numbers.     

Critical scattering and pionic instabilities in heavy ion collisions

We investigate the effect of collective instabilities in heavy ion collisions. The focus is on critical scattering phenomena associated with pionic instabilities. The decay rate Γ of excited many-body systems is calculated in RPA. Γ is shown to give the rate of spontaneous “phonon” pair production. We express Γ as a sum of a collective, Γ_col, and a scattering, Γ_scat, rate. Γ_col is the pair production rate of phonons in unstable states. In the case of pionic instabilities, Γ_col is the condensation rate of π⁺π^? and π⁰π⁰ pairs into unstable states. Γ_scat is the pair production rate of phonons in the particle-hole excitation region and gives the two-body scattering rate in the medium. An effective (density-dependent) two-body cross section is obtained. The difference between critical scattering of external particles in a system near equilibrium and that of constituents of systems far from equilibrium is investigated. A model calculation suggests the existence of pionic instabilities in heavy ion collisions. Growth rates of unstable modes and the effective cross sections displaying critical scattering are calculated. Finally, we estimate Γ_scat and Γ_col.     

Crystal packing of TCNQ anion pi-radicals governed by intermolecular covalent pi-pi bonding: DFT calculations and statistical analysis of crystal structures

On the basis of a thorough Cambridge Structural Database survey, we present a statistical analysis of the packing of TCNQ anion pi-radicals in TCNQ charge transfer salts, which reveals three packing motifs between neighboring TCNQs: one with a zero longitudinal offset and an approximate 1 A transversal offset, another with an approximate 2 A longitudinal offset and zero transversal offset, and the third with a relatively long sigma-bond in the length of r = 1.6-1.7 A connecting two TCNQ fragments. Along with the statistical analysis of the crystal structures, we also present density functional theory calculations of the total energy, covalent pi-pi bonding interaction energy, and Coulombic repulsion energy for the [TCNQ](2)(2-)pi-dimers with various packing geometries. We find that the interactions between TCNQ anion pi-radicals include contributions from intermolecular covalent pi-pi bonding interaction and local dipole repulsions, in addition to Coulombic repulsion, van der Waals and the attractive electrostatic forces between counter-cations and TCNQ anions pointed out recently by other groups for TCNE anion radicals. We describe an approximate formula for intermolecular interaction energy, E(int) = E(coul) + E(bond) + E(vdW), for systems in vacuum, while in the solid state E(coul) is compensated by the attractive electrostatic forces between counter-cations and TCNQ anions. We conclude that the crystal packing of TCNQ molecules in their charge transfer salts is predominantly determined by the intermolecular covalent pi-pi bonding term, E(bond).     

Shear and extensional rheology of solutions of mixtures of poly(ethylene oxide) and anionic surfactants in ionic environments

Interactions between a high molecular weight poly(ethylene oxide) (PEO) and the anionic surfactant sodium dodecyl benzene sulfonate (SDBS) in aqueous solutions were investigated by shear and extensional rheometry. Results for mixtures between PEO and sodium dodecyl sulfate (SDS) are also presented for comparison purposes. Addition of anionic surfactants to PEO solutions above the critical aggregation concentration (CAC), at which micellar aggregates attach to the polymer chain, results in an increase in shear viscosity due to PEO coil expansion, and a strengthening of interchain interactions. In extensional flows, these interactions result in a decrease of the critical shear rate for the onset of the characteristic extension thickening of the PEO solutions that is due to transient entanglements of polymer molecules. The relaxation times associated with these transient entanglements are not directly proportional to the shear viscosity of the solutions, but rather vary more rapidly with surfactant concentration. In the presence of an electrolyte, coil contraction results in lower shear viscosities and a decrease in the extension thickening effects at surfactant concentrations just beyond the CAC. The relaxation times associated with transient entanglement reach a minimum at the same surfactant concentration as the shear viscosity, which indicates that coil contraction is responsible for the observed effects in both types of flow. However, the increase in extensional-flow entanglement relaxation times is much more abrupt than the decrease in shear viscosity. All these results point to a greater sensitivity of extensional flows on the molecular conformation of PEO/surfactant complexes.     

Theoretical analysis of intermolecular covalent pi-pi bonding and magnetic properties of phenalenyl and spiro-biphenalenyl radical pi-dimers

Singlet-triplet splittings DeltaEST and intermolecular covalent pi-pi bonding characteristics of the prototypical phenalenyl pi-dimer and eight spiro-biphenalenyl radical pi-dimer structures are analyzed with the aid of restricted and unrestricted density functional theory calculations and paramagnetic susceptibility data fitted using the Bleaney-Bowers dimer model and the Curie-Weiss model. Single determinant approximations for DeltaEST as a function of transfer integrals and on-site Coulomb repulsion energy are presented for the two-electron two-site pi-dimers of phenalenyls and the two-electron four-site pi-dimers of spiro-biphenalenyl radicals. Within the range of intermolecular separation of 3.12相似文献   

Local modifications of single-wall carbon nanotubes induced by bond formation with encapsulated fullerenes

Defected fullerenes in nanopeapods form bonds with the encapsulating single-walled carbon nanotubes when irradiated by an electron beam leading to changes in the guest (fullerene) and the host (nanotube). Intrinsic reaction coordinate (IRC) analysis based on B3LYP hybrid density functional theory shows that a C1-C59 defect with a single protruding C atom is initially formed from the C60(Ih) cage. The high activation energy for this step (8.37 eV (193.0 kcal/mol)), being assumed to be accessible during irradiation, is lower than that of the Stone-Wales rearrangement on the sp2 network. The binding of the defected fullerene to the nanotube is preferential, orthogonal bonds relative to the tube axis being slightly preferred. Because of the covalent bonds formed between the guest and host, the carbon network on the nanotube is locally perturbed in the vicinity of the binding site. As a result of the new bonds, bisnorcaradiene-like as well as quinonoid-like patterns appear near the binding site. These results are interpreted using orbital interaction and Clar diagram arguments. The changes in the bonding pattern on the nanotube should be significant in further functionalization of carbon nanotubes.