The diuranium(III) compound [UN′′2]2(μ‐η6:η6‐C6H6) (N′′=N(SiMe3)2) has been studied using variable, high‐pressure single‐crystal X‐ray crystallography, and density functional theory . In this compound, the low‐coordinate metal cations are coupled through π‐ and δ‐symmetric arene overlap and show close metal CH contacts with the flexible methyl CH groups of the sterically encumbered amido ligands. The metal–metal separation decreases with increasing pressure, but the most significant structural changes are to the close contacts between ligand CH bonds and the U centers. Although the interatomic distances are suggestive of agostic‐type interactions between the U and ligand peripheral CH groups, QTAIM (quantum theory of atoms‐in‐molecules) computational analysis suggests that there is no such interaction at ambient pressure. However, QTAIM and NBO analyses indicate that the interaction becomes agostic at 3.2 GPa. 相似文献
Alcohol oxidation and self‐assembly: the in situ oxidation of hydroxyl functional groups to quinone groups promotes the formation of enhanced hydrogen bonds and allows reorganization of the resulting supramolecular self‐assemblies, which evolve from a weakly bound dense phase to a strongly bound nanoporous open structure (see picture).
The study of the ecotoxicity in two industrial waste materials and the relationships with the organic parameters has been conducted. Foundry sludge and olive mill waste have been used as industrial waste materials with organic or mixed character. Stabilisation/solidification (S/S) and advanced oxidation (AOP) processes have been carried out in order to treat both foundry sludge and olive mill waste. Analysis of ecotoxicity, total organic carbon, COD and phenol index have been evaluated in the untreated waste and end-products. The results of the treated samples allow obtaining the best formulations in both processes. The best formulations in the immobilisation process have been obtained with Portland cement and black carbon, activated carbon or foundry sand ashes. In the AOP process, ozone concentrations above 35 mg/l and reaction times equal to 120 minutes have been the optimal variables. The relationships between the organic parameters and the ecotoxicity of the samples have been studied in this paper. Furthermore, the global organic parameters have been studied in relation to the phenolic compounds. Lineal and logarithmic expressions have been obtained between the total organic carbon and phenol index and the ecotoxicity of the samples related to the organic parameters, respectively. Ecotoxicity of the samples with Vibrio fischeri is recommended as a very promising biotest for the study of the characterisation and the evaluation of the treatment of organic and mixed character waste and total organic carbon is recommended as global organic parameter in the treatment of foundry sludge. 相似文献
Ab initio methods have been used to characterise the lowest energy potential energy surfaces of 1BCl3(2+) and 3BCl3(2+). The methods used are MP2, CCSD, CCSD(T) and MCSCF with 6-311G(d), cc-pVTZ and aug-cc-pVTZ basis sets. While the singlet surface is relatively straight-forward, the triplet surface is very complicated, with many stationary points in close energetic proximity. The singlet surface can fragment to the following products (1BCl + 1Cl+ + 1Cl+), (1Cl+ + 1B+ + 1Cl2), (2BCl+ + 2Cl), while the triplet surface can fragment to (1BCl2+ + 3Cl+) and (2BCl2(2+) + 2Cl). 2BCl2(2+) can further fragment to (1Cl+ + 2BCl+). These results are in good agreement with previous experimental data from coincidence mass spectroscopy. [symbol: see text]1 diagnostic values have been calculated for all of the stationary points of BCl3(2+), using the method of Lee and Taylor. These data, together with CCSD/CCSD(T) energy differences and MCSCF calculations, are used to conclude that most of the stationary points on the singlet surface are well represented using single reference methods. The stationary points of the triplet system have [symbol: see text]1 diagnostic values greater than those for the singlet system, as expected when using the closed-shell [symbol: see text]1 diagnostic method of Lee and Taylor. However, all of the structures have acceptable single reference wavefunctions if the open-shell upper limit of Rienstra-Kiracofe et al. (0.045) is used, a conclusion fully supported by CCSD/CCSD(T) energy differences. CCSD(T) energies determined for the fragmentation asymptotes have been compared with experimental data collated from the NIST Theoretical and Scientific Data website, and the generally very good agreement between theory and experiment reinforces the reliability of the CCSD(T) method. 相似文献
Gradient corrected density functional theory has been used to calculate the geometric and electronic structures of the family of molecules [UO2(H2O)m(OH)n](2 - n) (n + m = 5). Comparisons are made with previous experimental and theoretical structural and spectroscopic data. r(U-O(yl)) is found to lengthen as water molecules are replaced by hydroxides in the equatorial plane, and the nu(sym) and nu(asym) uranyl vibrational wavenumbers decrease correspondingly. GGA functionals (BP86, PW91 and PBE) are generally found to perform better for the cationic complexes than for the anions. The inclusion of solvent effects using continuum models leads to spurious low frequency imaginary vibrational modes and overall poorer agreement with experimental data for nu(sym) and nu(asym). Analysis of the molecular orbital structure is performed in order to trace the origin of the lengthening and weakening of the U-O(yl) bond as waters are replaced by hydroxides. No evidence is found to support previous suggestions of a competition for U 6d atomic orbitals in U-O(yl) and U-O(hydroxide)pi bonding. Rather, the lengthening and weakening of U-O(yl) is attributed to reduced ionic bonding generated in part by the sigma-donating ability of the hydroxide ligands. 相似文献
In this paper fluid models for heterogeneous multiplexed traffic are considered. First, some extensions to the general theory applicable to superposed, time-reversible Markovian Rate Processes are given. These refer to the connection between performance metrics, the consideration for singular systems and the continuity of the solution, with respect to the system parameters. The general framework is then carried over to the heterogeneous multiplexing of ON/OFF sources. By combining the general theory with the special structure of the ON/OFF sources several important facets of this structure are highlighted. As a result, more powerful methods that improve computation speed, stability and ease of implementation are produced. More specifically, the numerical part of the method is reduced to a solution of a nonlinear equation per system eigenvalue. The solution is obtainable through a variant of the (locally quadratically convergent) Newton method. For this method, easily computable starting values that guarantee convergence are given. In addition, explicit expressions for the eigenvectors are provided with the potentially unstable quantities factored-out. The paper also provides explicit and stably computable formulae for upper bounds to the coefficients of the spectral components, present in the expressions for the performance measures of interest. Moreover, the paper proves a partial ordering property for the system eigenvalues and presents an algorithm that performs full ordering on-line. This, in many cases, results in a great reduction to the amount of computation, without any significant loss of precision. Lastly, the particular case of heterogeneity where the differences are only identified in the rates within bursts is seen to have features resembling homogeneous systems. The possibility to substitute an equivalent homogeneous system of reduced order, for the original heterogeneous one is addressed. 相似文献
We introduce a model of two coupled reaction-diffusion equations to describe the dynamics and propagation of flame fronts in random media. The model incorporates heat diffusion, its dissipation, and its production through coupling to the background reactant density. We first show analytically and numerically that there is a finite critical value of the background density below which the front associated with the temperature field stops propagating. The critical exponents associated with this transition are shown to be consistent with meanfield theory of percolation. Second, we study the kinetic roughening associated with a moving planar flame front above the critical density. By numerically calculating the time-dependent width and equal-time height correlation function of the front, we demonstrate that the roughening process belongs to the universality class of the Kardar-Parisi-Zhang interface equation. Finally, we show how this interface equation can be analytically derived from our model in the limit of almost uniform background density. 相似文献
The influence of the anisotropic hyperfine interaction on the 14N electron-nuclear double resonance/electron spin echo envelope modulation spectra is studied by approximate analytical and graphical methods for the case of the isotropic g-factor. The suggested determination of the modified characteristic directions of the magnetic field due to anisotropy enhances the insight in the structural details of the system and analytical solutions of the secular equation for these conditions are derived. The graphical method, previously used for the analysis of the orientation dependence of the 14N nuclear-transition frequencies in orientation-disordered samples for isotropic hyperfine interaction is extended to the case of arbitrary anisotropic hyperfine tensor. The above analytical and graphical methods are illustrated and tested against exact simulations in two practically important cases: (i) isotropic hyperfine interaction (hfi) exceeding other nuclear interactions in nuclear spin Hamiltonian. (ii) Cancellation of the isotropic part of the hfi. 相似文献