Synthesis, spectroscopy, and characterization of some bis-nicotinamide metal(II) dihalide complexes

We report synthesis of six new bis-nicotinamide metal(II) dihalide complexes [M(nia)(2)Cl(2); M = Mn, Co; nia:nicotinamide, M(nia)(2)Br(2); M = Mn, Hg; M(nia)(2)I(2); M = Cd, Cu], and their characterization by combining infrared spectroscopy with density functional theory (DFT) calculations. Infrared spectra indicate that ring-nitrogen is the active donor cite, and the atomic structure of the complexes is determined to be polymeric octahedral or distorted polymeric octahedral. Spin polarized electronic ground state is obtained for Mn, Co, and Cu halide complexes. The colors of the complexes also support the conclusion of octahedral coordination around the metal atoms, in agreement with DFT results.     

Quantum chemical computational studies on 5-(4-bromophenylamino)-2-methylsulfanylmethyl-2H-1,2,3-triazol-4-carboxylic acid ethyl ester

The optimized molecular geometry, vibrational frequencies, and gauge including atomic orbital (GIAO) (1)H and (13)C NMR shift values of 5-(4-bromophenylamino)-2-methylsulfanylmethyl-2H-1,2,3-triazol-4-carboxylic acid ethyl ester have been calculated by using Hartree-Fock (HF) and density functional method (DFT/B3LYP) with 6-31G(d), 6-31G(d,p) and LANL2DZ basis sets. The optimized molecular geometric parameters were presented and compared with the data obtained from X-ray diffraction. In order to fit the calculated harmonic wavenumbers to the experimentally observed ones, scaled quantum mechanics force field (SQM FF) methodology was proceeded. Correlation factors between the experimental and calculated (1)H chemical shift values of the title compound in vacuum and in CHCl(3) solution by using the conductor-like screening continuum solvation model (COSMO) were reported. The calculated results showed that the optimized geometry well reproduces the crystal structure. The theoretical vibrational frequencies and chemical shifts are in very good agreement with the experimental data. In solvent media the energetic behavior of the title compound was also examined by using the B3LYP method with the 6-31G(d) basis set, applying the COSMO model. The obtained results indicated that the total energy of the title compound decreases with increasing polarity of the solvent. Furthermore, molecular electrostatic potential (MEP), natural bond orbital (NBO) and frontier molecular orbitals (FMOs) of the title compound were performed by the B3LYP/LANL2DZ method, and also thermodynamic parameters for the title compound were calculated at all the HF and B3LYP levels.     

A nonlinear visco-elastoplastic impact model and the coefficient of restitution

A visco-elastoplastic model for the impact between a compact body and a composite target is presented. The model is a combination of a nonlinear contact law that includes energy loss due to plastic deformation and a viscous element that accounts for energy losses due to wave propagation and/or damping. The governing nonlinear equations are solved numerically to obtain the response. A piecewise linear version of the model is also presented, which facilitates analytical solution. The model predictions are compared to those of the well-known and commonly used Hunt–Crossley model. The effects of the various impact parameters, such as impactor mass, velocity, plasticity, and damping, on the impact response and coefficient of restitution are investigated. The model appears to be suitable for a wide range of impact situations, with parameters that are well defined and easily calculated or measured. Furthermore, the resulting coefficient of restitution is shown to be a function of impact velocity and damping, as confirmed by published experimental data.     

Optimal residuals and the Dahlquist test problem

Numerical Algorithms - We show how to compute the optimal relative backward error for the numerical solution of the Dahlquist test problem by one-step methods. This is an example of a general...     

Structure of 4,4′-butane-(1,4,7-three-p-tolylsulphonyl-1,4,7-three amine) diphthalonitrile

Abstract

The crystal structure of the title compound, C₄₁ H₃₅ N₇ O₆ S₃ was determined as monoclinic by single crystal X-Ray diffraction technique. The molecular structure was identified by IR, ¹H-NMR, ¹³C-NMR and elemental analysis. The crystal parameters of this compound are as follows: monoclinic P 2 1/n, a = 12.694(2) Å, b = 26.204(2) Å, c = 13.005(2) Å, β = 102.95(2)°, V = 4216.02(1) Å.³, Z = 4, Dx = 1.289 g/cm³, F(000) = 1704, λ (MoKα) = 0.71070 Å, μ = 0.2 mm^?1. The structure was solved by SHELXS-97 and refined by SHELXL-97. R = 0.06 for 3178 observed reflections with I > 2σ (I).     

Anomalous field dependence of muon Knight shift and line width in the singlet ground state compound PrCu2

We report on ZF and TF‐studies of PrCu₂ above the induced Jahn–Teller transition at 7.3 K. Generally a two‐component signal is found, one showing inhomogeneous the other one homogeneous, temperature dependent line broadening. In ZF the former component is well represented by a Gaussian Kubo–Toyabe function with \varDelta \simeq 6.5\,μs^-1 at 7.5 K, corresponding to a field width of 76 G. This is about 30 times larger than what is calculated to arise from the ¹⁴¹Pr‐nuclear dipole moments alone, pointing to strong hyperfine enhanced features. TF‐field scans at 12 K revealed that the enhancement is suppressed in external fields exceeding 1 kG. In parallel the Knight shift drops from very large values well above 10% at 100 G to shifts of the order of 1% above 1 kG. A scaling of the Knight shifts with the corresponding relaxation rates seems to imply that the strange field dependence below 1 kG is associated with the magnetic susceptibility of the muons’s nearest neighbour Pr³⁺‐ions, a result for which we have no explanation yet to offer. This revised version was published online in July 2006 with corrections to the Cover Date.     

SVL fluorescence and duschinskii effect in the S1 state of pyridine

SVL fluorescence spectra from principal bands in the S₁ state of pyridine h₅ and -d₅ were measured. A large displacement of the normal coordinate origin of v_6a and the Duschinskii rotation of v_10a and v_16a were established.     

Heating mechanism in relation to the laser machining process

Laser workpiece interaction mechanism is an important phenomenon which will assist in the development of laser machining systems. The interaction mechanism is generally complicated and depends on the laser and workpiece properties. In the present study a mathematical analysis for the laser material removal by evaporation and radial ejection of liquid is carried out. In the analysis the time unsteady problem is solved and nucleation explosions are predicted.