Descripción: Langmuir probe measurements in an atmospheric pressure direct current (dc) plasma jet are reported. Sweeping probes were used. The experiment was carried out using a dc non-transferred arc torch with a rod-type cathode and an anode of 5 mm diameter. The torch was operated at a nominal power level of 15 kW with a nitrogen flow rate of 25 Nl min -1. A flat ion saturation region was found in the current-voltage curve of the probe. The ion saturation current to a cylindrical probe in a high-pressure non local thermal equilibrium (LTE) plasma was modeled. Thermal effects and ionization/recombination processes inside the probe perturbed region were taken into account. Averaged radial profiles of the electron and heavy particle temperatures as well as the electron density were obtained. An electron temperature around 11 000 K, a heavy particle temperature around 9500 K and an electron density of about 4 × 10 22 m -3, were found at the jet centre at 3.5 mm downstream from the torch exit. Large deviations from kinetic equilibrium were found throughout the plasma jet. The electron and heavy particle temperature profiles showed good agreement with those reported in the literature by using spectroscopic techniques. It was also found that the temperature radial profile based on LTE was very close to that of the electrons. The calculations have shown that this method is particularly useful for studying spraying-type plasma jets characterized by electron temperatures in the range 9000-14 000 K. © 2012 American Institute of Physics.

Descripción: We investigate the importance of relativistic effects on NMR shielding constants and chemical shifts of linear HgL2 (L = Cl, Br, I, CH 3) compounds using three different relativistic methods: the fully relativistic four-component approach and the two-component approximations, linear response elimination of small component (LR-ESC) and zeroth-order regular approximation (ZORA). LR-ESC reproduces successfully the four-component results for the C shielding constant in Hg(CH3)2 within 6 ppm, but fails to reproduce the Hg shielding constants and chemical shifts. The latter is mainly due to an underestimation of the change in spin-orbit contribution. Even though ZORA underestimates the absolute Hg NMR shielding constants by ∼2100 ppm, the differences between Hg chemical shift values obtained using ZORA and the four-component approach without spin-density contribution to the exchange-correlation (XC) kernel are less than 60 ppm for all compounds using three different functionals, BP86, B3LYP, and PBE0. However, larger deviations (up to 366 ppm) occur for Hg chemical shifts in HgBr 2 and HgI2 when ZORA results are compared with four-component calculations with non-collinear spin-density contribution to the XC kernel. For the ZORA calculations it is necessary to use large basis sets (QZ4P) and the TZ2P basis set may give errors of ∼500 ppm for the Hg chemical shifts, despite deceivingly good agreement with experimental data. A Gaussian nucleus model for the Coulomb potential reduces the Hg shielding constants by ∼100-500 ppm and the Hg chemical shifts by 1-143 ppm compared to the point nucleus model depending on the atomic number Z of the coordinating atom and the level of theory. The effect on the shielding constants of the lighter nuclei (C, Cl, Br, I) is, however, negligible. © 2011 American Institute of Physics.