The aim of this work was to determine and understand the origin of the electronic properties of Mn(IV) complexes, especially the zero-field splitting (ZFS), through a combined experimental and theoretical investigation on five well-characterized mononuclear octahedral Mn(IV) compounds, with various coordination spheres (N6, N3O3, N2O4 in both trans (trans-N2O4) and cis configurations (cis-N2O4) and O4S2). High-frequency and -field EPR (HFEPR) spectroscopy has been applied to determine the ZFS parameters of two of these compounds, MnL(trans-N2O4) and MnL(O4S2). While at X-band EPR, the axial-component of the ZFS tensor, D, was estimated to be +0.47 cm(-1) for MnL(O4S2), and a D-value of +2.289(5) cm(-1) was determined by HFEPR, which is the largest D-magnitude ever measured for a Mn(IV) complex. A moderate D value of -0.997(6) cm(-1) has been found for MnL(trans-N2O4). Quantum chemical calculations based on two theoretical frameworks (the Density Functional Theory based on a coupled perturbed approach (CP-DFT) and the hybrid Ligand-Field DFT (LF-DFT)) have been performed to define appropriate methodologies to calculate the ZFS tensor for Mn(IV) centers, to predict the orientation of the magnetic axes with respect to the molecular ones, and to define and quantify the physical origin of the different contributions to the ZFS. Except in the case of MnL(trans-N2O4), the experimental and calculated D values are in good agreement, and the sign of D is well predicted, LF-DFT being more satisfactory than CP-DFT. The calculations performed on MnL(cis-N2O4) are consistent with the orientation of the principal anisotropic axis determined by single-crystal EPR, validating the calculated ZFS tensor orientation. The different contributions to D were analyzed demonstrating that the d-d transitions mainly govern D in Mn(IV) ion. However, a deep analysis evidences that many factors enter into the game, explaining why no obvious magnetostructural correlations can be drawn in this series of Mn(IV) complexes.

No abstract

No abstract

No abstract

No abstract

The specific heat of multi-walled carbon nanotubes (MWCNTs) with a low defectiveness and with a low content of inorganic impurities has been measured in the temperature range from 1.8 to 275 K by the thermal relaxation method. The elemental composition and morphology of the MWCNTs were determined using scanning electron microscopy analysis and energy dispersion x-ray spectroscopy. The MWCNTs were prepared by chemical catalytic vapor deposition and have mean diameters from 7 nm up to 18 nm and lengths in some tens of microns. MWCNTs purity is over 99.4 at.%. The mass of the samples ranged from 2-4 mg. It was found that the temperature dependence of the specific heat of the MWCNTs differs significantly from other carbon materials (graphene, bundles of SWCNTs, graphite, diamond) at low temperatures. The specific heat of MWCNTs systematically decreases with increasing diameter of the tubes at low temperatures. The character of the temperature dependence of the specific heat of the MWCNTs with different diameters demonstrates the manifestation of different dimensions from 1D to 3D, depending on the temperature regions. The crossover temperatures are about 6 and 40 K. In the vicinity of these temperatures, a hysteresis is observed.

In the paper the reactivity characteristics of the core of the large sodium fast reactor Superphenix (SPX) were evaluated and compared with available experimental data. The analysis was performed using the TRACE system code modified for the fast reactor applications. The simplified core model was developed aiming to overcome the lack of detailed information on design and realistic core conditions. Point Kinetics neutronic model with all relevant reactivity feedbacks was used to calculate transient power. The paper focuses on challenging issue of modelling of the transient thermal responses of primary system structural elements resulting in reactivity feedbacks specific to such large fast reactor which cannot be neglected. For these effects, the model was equipped with dedicated heat structures to reproduce important feedbacks due to vessel wall, diagrid, strongback, control rod drive lines thermal expansion. Peculiarly, application of the model was considered for a whole range of core conditions from zero power to 100% nominal. The developed core model allowed reproducing satisfactorily the core reactivity balance between zero power at 180?C and full power conditions. Additionally, the reactivity coefficients k, g, h at three power levels were calculated and satisfactory agreement with experimental measurements was also observed. The study demonstrated feasibility of application of relatively simple model with adjusted parameters for analysis of different conditions of very complex system.

In the paper, the specification of a new neutronics benchmark for a large Sodium cooled Fast Reactor core and results of modelling by different participants are presented. The neutronics benchmark describes the core of the French sodium cooled reactor Superphénix at its startup configuration, which in particular was used for experimental measurement of reactivity characteristics. The benchmark consists of the detailed heterogeneous core specification for neutronic analysis and results of the reference solution. Different core geometries and thermal conditions from cold “as fabricated” up to full power were considered. The reference Monte Carlo solution of Serpent 2 includes data on multiplication factor, power distribution, axial and radial reaction rates distribution, reactivity coefficients and safety characteristics, control rods worth, kinetic data. The results of modelling with seven other solutions using deterministic and Monte Carlo methods are also presented and compared to the reference solution. The comparisons results demonstrate appropriate agreement of evaluated characteristics. The neutronics results will be used in the second phase of the benchmark for evaluation of transient behaviour of the core.