A relativistic DFT study of magnetic exchange coupling in ketimide bimetallic uranium(IV) complexes

Magnetic exchange couplings in bis(ketimide) binuclear U^IV/U^IV complexes [Cp′₂UCl]₂(μ-ketimide) diuranium(IV) and [(C₅H₅)₂(Cl)An]₂(μ-ketimide) (Cp′ = C₅Me₄Et; ketimide = N=CMe-(C₆H₄)-MeC=N) have been investigated computationally using relativistic density functional theory (DFT) combined with the broken symmetry (BS) approach. Using the B3LYP hybrid functional, the BS ground state of these U^IV/U^IV 5f ²–5f ² complexes has been found of lower energy than the high spin (HS) quintet state, indicating an antiferromagnetic character (estimated coupling constant |J| < 5 cm⁻¹) which has not yet been evidenced unambiguously experimentally. On the contrary, the BP86 GGA functional overestimates greatly the antiferromagnetic character of the complexes (|J| > 100 cm⁻¹). As recently reported for para-bis(imido) [(C₅H₅)₃U]₂(μ-imido) uranium(V) complex, spin polarization is mainly responsible for the antiferromagnetic coupling through the π-network orbital pathway within the bis(ketimide) bridge. Furthermore, spin polarization is exalted by the combined roles of the 5f metal orbitals and of the π-conjugated ketimide bridging ligand which permit electronic communication between the two uranium atoms albeit separated by a distance of the order of 10 ?. The MO analysis clarifies which MOs contribute to the antiferromagnetic coupling in the binuclear complexes under consideration and brings to light the 5f orbitals driving contribution.     

Synthesis of bismuth mixed oxide by thermal decomposition of a coprecipitate precursor

Bismuth mixed oxide powders were prepared by oxalate coprecipitation process. The thermal decomposition behaviour of the coprecipitate precursors has been followed by thermal analysis (TG-DTA) and FTIR spectroscopy. During the decomposition of the precursor, several intermediates species were detected and a mechanism of formation of mixed oxide by this method is proposed. After the thermal treatment, the precursor obtained of suggested formula Ca₃[Bi₆O₆(C₂O₄)₄(OH)₃NO₃]0.5H₂O, has led to the formation of CaBi₂O₄ at shorter reaction time than the traditional ceramic method. In order to consolidate the results, the coprecipitation in absence of oxalic precipitant under the same conditions was examined. XRD and scanning electron spectroscopy were used to study particles sizes and morphology.     

Classification of torsion-free genus zero congruence groups

We study and classify all torsion-free genus zero congruence subgroups of the modular group.

     

A ruthenium(II) complex with p‐cymene and (S)‐2‐(anilinomethyl)pyrrolidine

The title compound, [(S)‐2‐(anilino­methyl)­pyrrolidine‐N,N′]‐chloro(η⁶‐para‐cymene)­ruthenium(II) chloride, [RuCl‐(C₁₀H₁₄)(C₁₁H₁₆N₂)]Cl, has been synthesized by the reaction of [RuCl₂(p‐cymene)]₂ (p‐cymene is para‐iso­propyl­toluene) with (S)‐2‐(anilinomethyl)­pyrrolidine in triethyl­amine/2‐propanol. The Ru atom is in a pseudo‐tetrahedral environment coordinated by a chloride ligand, the aromatic hydro­carbon is linked in a η⁶ manner and the amine is linked via its two N atoms. The chloride anion is involved in hydrogen bonding with the di­amine moieties through N—H?Cl interactions, with N?Cl distances of 3.273 (4) and 3.352 (4) Å.     

On descent alternating direction method with LQP regularization for the structured variational inequalities

Optimization Letters - By reviewing the Logarithmic–quadratic proximal (LQP) method, in this paper we suggest and analyze a new LQP alternating direction scheme for the separable constrained...     

A new projection and contraction method for linear variational inequalities

In this paper, we presented a new projection and contraction method for linear variational inequalities, which can be regarded as an extension of He's method. The proposed method includes several new methods as special cases. We used a self-adaptive technique to adjust parameter β at each iteration. This method is simple, the global convergence is proved under the same assumptions as He's method. Some preliminary computational results are given to illustrate the efficiency of the proposed method.