Rotational spectrum and structure of the carbonyl sulfide-trifluoromethane weakly bound dimer

Pure rotational spectra of five isotopomers of the 1:1 weakly bound complex formed between carbonyl sulfide and trifluoromethane (TFM) have been measured using Fourier transform microwave spectroscopy. The experimental rotational constants and dipole moment components are consistent with a structure of C(s) symmetry in which the dipole moment vectors of OCS and HCF(3) are aligned antiparallel and at an angle of about 40 degrees and with a center of mass separation of 3.965(26) A. The derived H...O distance is 2.90(5) A, which is up to 0.6 A longer than is seen in other similar TFM complexes exhibiting C-H...O interactions. Ab initio calculations at the MP2/6-311++G(2d,2p) level give a structure with rotational constants that are in reasonable agreement with those of the normal isotopic species.     

η-Alkynyl and vinylidene transition metal complexes: 10. Reaction of the metal-acetylide [(η-C5H5)(CO)(NO)W---CC---C(CH3)3]Li with 1,2-diiodoethane as electrophile and with various nucleophiles

Treatment of the η¹-acetylide complex [(η⁵-C₅H₅)(CO)(NO)W---CC---C(CH₃)₃]Li (4) with 1,2-diiodoethane in THF at −78 °C, followed by the addition of Li---CC---R [R=C(CH₃)₃, C₆H₅, Si(CH₃)₃, 6a–6c] or n-C₄H₉Li and protonation with H₂O, afforded the corresponding oxametallacyclopentadienyl complexes (η⁵-C₅H₅)W(I)(NO)[η²-O=C(CC---R)CH=CC(CH₃)₃] (7a–7c), 8c and (η⁵-C₅H₅)W(I)(NO)[η²-O=C(n-C₄H₉)CH=CC(CH₃)₃] (9). The formation of these metallafuran derivatives is rationalized by the electrophilic attack of 1,2-diiodoethane onto the metal center of 4 to form first the neutral complex [(η⁵-C₅H₅)(I)(CO)(NO)W---CC---C(CH₃)₃] (5). Subsequent nucleophilic addition of Li---CC---R 6a–6c or n-C₄H₉Li and a reductive elimination step followed by protonation leads to the products 7a–7c and 9. One reaction intermediate could be trapped with CF₃SO₃CH₃ and characterized by a crystal structure analysis. The identity of another intermediate was established by infrared spectroscopic data. The oxametallacyclopentadienyl complex 10 forms in the presence of excess 1,2-diiodoethane through an alternative pathway and crystallizes as a clathrate containing iodine.     

Quantitatively probing the means of controlling nanoparticle assembly on surfaces

As a means of developing a simple, cost-effective, and reliable method for probing nanoparticle behavior, we have used atomic force microscopy to gain a quantitative 3D visual representation of the deposition patterns of citrate-capped Au nanoparticles on a substrate as a function of (a) sample preparation, (b) the choice of substrate, (c) the dispersion solvent, and (d) the number of loading steps. Specifically, we have found that all four parameters can be independently controlled and manipulated in order to alter the resulting pattern and quantity of as-deposited nanoparticles. From these data, the sample preparation technique appears to influence deposition patterns most broadly, and the dispersion solvent is the most convenient parameter to use in tuning the quantity of nanoparticles deposited onto the surface under spin-coating conditions. Indeed, we have quantitatively measured the effect of surface coverage for both mica and silicon substrates under preparation techniques associated with (i) evaporation under ambient air, (ii) heat treatment, and (iii) spin-coating preparation conditions. In addition, we have observed a decrease in nanoparticle adhesion to a substrate when the ethylene glycol content of the colloidal dispersion solvent is increased, which had the effect of decreasing interparticle-substrate interactions. Finally, we have shown that substrates prepared by these diverse techniques have potential applicability in surface-enhanced Raman spectroscopy.     

Generalized transformation for decorated spin models

The paper discusses the transformation of decorated Ising models into an effective undecorated spin model, using the most general Hamiltonian for interacting Ising models including a long range and high order interactions. The inverse of a Vandermonde matrix with equidistant nodes [−s,s] is used to obtain an analytical expression of the transformation. This kind of transformation is very useful to obtain the partition function of decorated systems. The method presented by Fisher is also extended, in order to obtain the correlation functions of the decorated Ising models transforming into an effective undecorated Ising model. We apply this transformation to a particular mixed spin-(1/2, 1) and (1/2, 2) square lattice with only nearest site interaction. This model could be transformed into an effective uniform spin-S square lattice with nearest and next-nearest interaction, furthermore the effective Hamiltonian also includes combinations of three-body and four-body interactions; in particular we considered spin 1 and 2.     

Quasi-elastic neutrino-nucleus reactions

The quasi-elastic contribution of the nuclear inclusive electron scattering model developed in [A. Gil, J. Nieves, and E. Oset: Nucl. Phys. A 627 (1997) 543] is extended to the study of electroweak charged current induced nuclear reactions at intermediate energies of interest for future neutrino oscillation experiments. The model accounts for long-range nuclear (RPA) correlations, final state interaction and Coulomb corrections. RPA correlations are shown to play a crucial role in the whole range of neutrino energies, up to 500 MeV, studied in this work. Predictions for inclusive muon capture for different nuclei, and for the reactions ¹²C(ν _μ , μ ₋)X and ¹²C(ν _e, e⁻)X near threshold are also given. Presented by M. Valverde at the Workshop on calculation of double-beta-decay matrix elements (MEDEX’05), Corfu, Greece, September 26–29, 2005.     

Column switching liquid chromatography and post-column photochemically fluorescence detection to determine imidacloprid and 6-chloronicotinic acid in honeybees

The determination of imidacloprid and its main metabolite (6-chloronicotinic acid) in honeybees was performed by liquid chromatography with post-column photochemical derivatisation in alkaline medium and fluorescence detection. The compounds were extracted from honeybees with acetone under ultrasound conditions prior to liquid-liquid partition with dichloromethane. The separation of extract components was performed using a 50 mm x 4.6 mm i.d. short column packed with 5 microm Aquasil C(18) using an acetonitrile:water gradient program as mobile phase. Injection of samples in 0.1 mol L(-1) H(3)PO(4)/KH(2)PO(4) buffer solution (pH 3) improved the chromatographic separation between the most polar components of matrix and the 6-chloronicotinic acid. Matrix components were removed to waste using an on-line clean-up method previously to post-column reaction. Limits of quantification were 0.3 and 5.0 microg L(-1) (corresponding to 1.2 and 20.0 microg kg(-1) in the honeybee sample) for imidacloprid and 6-chloronicotinic acid, respectively. The recovery was ranged from 80.2 to 91.7% with a relative standard deviation lower than 9.0%.     

An Improved Computational Strategy to Estimate Residual Stresses from Crack Compliance Data

The successive cracking (crack compliance) method is a destructive technique aimed at determination of residual stresses in various structural members. The laboratory measurements performed during extension of a crack are followed by a computational analysis. We propose a modification of the numerical approach in order to simplify the method and improve its accuracy. The basic idea of the proposed modification is to approximate plastic strains rather than the residual stresses directly. Furthermore, we use the goal oriented adaptive finite element method that generates optimal meshes for evaluation of strains at specific points.