Kinetics and mechanism of ligand substitution in bis(N-alkylsalicylaldiminato)oxovanadium(IV) complexes

Conventional and stopped-flow spectrophotometry was used to to study the kinetics of ligand substitution in a number of bis(N-alkylsalicylaldiminato)oxovanadium(IV) complexes (=VO(R-X-sal)(2)) by 1,1,1- trifluoropentane-2,4-dione (=Htfpd) in acetone, according to the following reaction: VO(R-X-sal)(2) + 2Htfpd --> VO(tfpd)(2) + 2R-X-salH. The acronym R-X-salH refers to N-alkylsalicylaldimines with substituents X = H, Cl, Br, CH(3), and NO(2) in the 5-position of the salicylaldehyde ring and N-alkyl groups R = n-propyl, isopropyl, phenyl, and neopentyl. Under excess conditions ([Htfpd](0) > [VO(R-X-sal)(2)](0)), substitution by Htfpd occurs in two observable steps, as characterized by pseudo-first-order rate constants k(obsd(1)) and k(obsd(2)). Both rate constants increase linearly with [Htfpd](0) according to k(obsd(1)) = k(s(1)) + k(1)[Htfpd](0) and k(obsd(2)) = k(s(2)) + k(2)[Htfpd](0), with k(s(1)) and k(s(2)) describing small contributions of solvent-initiated pathways. Depending on the nature of R and X, second-order rate constants k(1) and k(2) lie in the range 0.098-0.87 M(-1) s(-1) (k(1)) and 0.022-0.41 M(-1) s(-1) (k(2)) at 298 K. For ligand substitution in the system VO(n-propyl-sal)(2)/Htfpd, the activation parameters DeltaH++ = 35.8 +/- 2.8 kJ mol(-1) and DeltaS++ = -146 +/- 23 J K(-1) mol(-1) (k(1)) and DeltaH++ = 40.2 +/- 1.3 kJ mol(-1) and DeltaS++ = -142 +/- 11 J K(-1) mol(-1) (k(2)) were obtained. The Lewis acidity of the complexes VO(n-propyl-X-sal)(2) with X = H, Cl, Br, CH(3), and NO(2) was quantified spectrophotometrically by determination of equilibrium constant K(py), describing the formation of the adduct VO(n-propyl-X-sal)(2).pyridine. The adduct VO(tfpd)(2).n-propyl-salH, formed as product in the system VO(n-propyl-sal)(2)/Htfpd, was characterized by its dissociation constant, K(D) = (3.30 +/- 0.10) x 10(-3) M. The mechanism suggested for the two-step substitution process is based on initial formation of the adducts VO(R-X-sal)(2).Htfpd (step 1) and VO(R-X-sal)(tfpd).Htfpd (step 2).     

Investigations of the half-metallic behavior and the magnetic and thermodynamic properties of half-Heusler CoMnTe and RuMnTe compounds: A first-principles study

First-principles spin-polarized density functional theory （DFT） investigations of the structural, electronic, magnetic, and thermodynamics characteristics of the half-Heusler, CoMnTe and RuMnTe compounds are carried out. Calculations are accomplished within a state of the art full-potential （FP） linearized （L） augmented plane wave plus a local orbital （APW ＋ lo） computational approach framed within DFT. The generalized gradient approximation （GGA） parameterized by Perdew, Burke, and Ernzerhof （PBE） is implemented as an exchange correlation functional as a part of the total energy calculation. From the analysis of the calculated electronic band structure as well as the density of states for both compounds, a strong hybridization between d states of the higher valent transition metal （TM） atoms （Co, Ru） and lower valent TM atoms of （Mn） is observed. Furthermore, total and partial density of states （PDOS） of the ground state and the results of spin magnetic moments reveal that these compounds are both stable and ideal half-metallic ferromagnetic. The effects of the unit cell volume on the magnetic properties and half-metaliicity are crucial. It is worth noting that our computed results of the total spin magnetic moments, for CoMnTe equal to 4 ~tB and 3 p-B per unit cell for RuMnTe, nicely follow the rule μ2tot = Zt - 18. Using the quasi-harmonic Debye model, which considers the phononic effects, the effecs of pressure P and temperature T on the lattice parameter, bulk modulus, thermal expansion coefficient, Debye temperature, and heat capacity for these compounds are investigated for the first time.     

Third-order nonlinear optical properties of silver nanoparticles mediated by chitosan

Silver nanoparticles in chitosan medium were prepared by the chemical reduction method. Silver nitrate and hydrazine were used as the precursor and reducing agent in the present of chitosan as a natural host polymer. The samples are characterized by UV–visible spectroscopy, X-ray diffraction (XRD) and transmission electron microscopy (TEM). The measurements of nonlinear optical properties were defined by Z-scan technique using green CW laser beam operated at 532 nm wavelengths. Thermal effect has a dominant role in the overall material nonlinearity with CW laser. It is shown that the synthesized samples have a negative nonlinear refractive index.     

One-Dimensional Inverse Scattering Problem in Acoustics

We are concerned with the inverse scattering problem (ISP) in acoustics within the Marchenko inversion scheme. The quantum ISP is first discussed and applied in order to exhibit certain characteristics and application prospects of the method which could be useful in extending it to classical systems. We then consider the ISP in acoustics by assuming plane waves propagating in an elastic, isotropic, and linear medium. The wave equation is first transformed into a Schrödinger-like equation which can be brought into the Marchenko integral equation for the associated nonlocal kernel the solution of which provides us the full information of the underlying reflective profile. We apply the method in several model problems where the reflection coefficient of the multi-layer reflective medium is used as input to the ISP and in all cases we obtain excellent reproduction of the original structure of the scatterer. We then applied the inverse scattering scheme to construct profiles with certain predetermined reflection and transmission characteristics.     

The Asymptotic Expansion and Numerical Verification of Van der Pol's Equation

A technique is presented in this paper to verify the order of accuracy of asymptotic expansion of Van der Pol's equation. The technique is focused on using numerical solutions as an independent means of verifying the validity of asymptotic expansions.     

A simplified conjugation scheme for lower semi-continuous functions

We present two generalized conjugation schemes for lower semi-continuous functions defined on a real Banach space whose norm is Fréchet differentiable off the origin, and sketch their applications to optimization duality theory. Both approaches are based upon a new characterization of lower semi-continuous functions as pointwise suprema of a special class of continuous functions.     

Sedimentation rate inferred from 210Pb and 137Cs dating of three sediment cores at Itaipu reservoir (Paraná State,Brazil) the world’s second largest hydroelectricity producer

Journal of Radioanalytical and Nuclear Chemistry - This study provides the sedimentation rates (SR) of three drainage basins at Itaipu Reservoir (Paraná State, Brazil) by applying 210Pb and...