Hartree-Fock and density functional complete basis-set (CBS) predicted nuclear shielding anisotropy and shielding tensor components

The nuclear shielding anisotropy and shielding tensor components calculated using the hybrid density functional B3PW91 are reported for a model set of compounds comprised of N2, NH3, CH4, C2H4, HCN and CH3CN. An estimation of density functional theory (DFT) and Hartree-Fock complete basis-set limit (CBS) parameters from a 2 (3) point exact fit vs. least-squares fit was obtained with the cc-pVxZ and aug-cc-pVxZ basis sets (x=D, T, Q, 5, 6). Both Hartree-Fock- and DFT-predicted CBS shielding anisotropies and shielding tensor components of the model molecules were in reasonable agreement with available experimental data. The utility of using a limited CBS approach for calculating accurate anisotropic shielding parameters of larger molecules as complementary methods to solid-state NMR is proposed.     

Experimental and theoretical NMR and IR studies of the side-chain orientation effects on the backbone conformation of dehydrophenylalanine residue

Conformation of N-acetyl-(E)-dehydrophenylalanine N', N'-dimethylamide (Ac-(E)-ΔPhe-NMe(2)) in solution, a member of (E)-α, β-dehydroamino acids, was studied by NMR and infrared spectroscopy and the results were compared with those obtained for (Z) isomer. To support the spectroscopic interpretation, the Φ, Ψ potential energy surfaces were calculated at the MP2/6-31 + G(d,p) level of theory in chloroform solution modeled by the self-consistent reaction field-polarizable continuum model method. All minima were fully optimized by the MP2 method and their relative stabilities were analyzed in terms of π-conjugation, internal H-bonds and dipole interactions between carbonyl groups. The obtained NMR spectral features were compared with theoretical nuclear magnetic shieldings, calculated using Gauge Independent Atomic Orbitals (GIAO) approach and rescaled to theoretical chemical shifts using benzene as reference. The calculated indirect nuclear spin-spin coupling constants were compared with available experimental parameters.     

Studies on hydrogen diffusivity in iron aluminides using the Devanathan–Stachurski method

An electrolytic method for cathodic hydrogen saturation developed by Devanathan and Stachurski was successfully used to study hydrogen diffusivity in iron aluminides. Both an appropriate electrolyte and a saturating current density are required for this method. A proper form of the saturation curve was only obtained with 35% NaCl electrolyte, which removed the oxide film blocking hydrogen penetration without further corrosive destruction of the iron aluminide. The optimum saturation current density for determining the most reliable diffusivity was 1.91 A/cm², yielding D_eff,H = 4.81 × 10⁻⁶ cm²/s for Fe–40 at.% Al.     

Total-variation-diminishing implicit–explicit Runge–Kutta methods for the simulation of double-diffusive convection in astrophysics

We put forward the use of total-variation-diminishing (or more generally, strong stability preserving) implicit–explicit Runge–Kutta methods for the time integration of the equations of motion associated with the semiconvection problem in the simulation of stellar convection. The fully compressible Navier–Stokes equation, augmented by continuity and total energy equations, and an equation of state describing the relation between the thermodynamic quantities, is semi-discretized in space by essentially non-oscillatory schemes and dissipative finite difference methods. It is subsequently integrated in time by Runge–Kutta methods which are constructed such as to preserve the total variation diminishing (or strong stability) property satisfied by the spatial discretization coupled with the forward Euler method. We analyse the stability, accuracy and dissipativity of the time integrators and demonstrate that the most successful methods yield a substantial gain in computational efficiency as compared to classical explicit Runge–Kutta methods.