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1.
Journal of Experimental and Theoretical Physics - Exact eigenstates for a set of two or more interacting electronic orbits in a magnetic field are studied for a class of factorized Hamiltonians...  相似文献   
2.
The intrinsic properties of tetrazine as a π-anion receptor and as an on/off recognition probe merged with H-bond ability of an urea motif into a single architecture constitutes a new generation of well-defined anion receptors. Complexation properties directly benefit from the dual and synergistic contribution of tetrazine and urea. In this study, we report on the synthesis and assessment of binding properties to anions of diverse geometries. Association constants have been predicted by theoretical calculations and evaluated by multiple and complementary experimental techniques including electrospray-mass tandem spectroscopy, NMR, UV-visible, steady state fluorescence spectroscopies and time resolved fluorescence. These results provide the basis for a better understanding of both the complexation and the anion-dependent quenching mechanism.  相似文献   
3.
Although atomically precise polyhydrido copper nanoclusters are of prime interest for a variety of applications, they have so far remained scarce. Herein, this work describes the synthesis of a dithiophosphate-protected copper(I) hydride-rich nanocluster (NC), [Cu30H18{S2P(OnPr)2}12] ( 1H ), fully characterized by various spectroscopic methods and single-crystal X-ray diffraction. The X-ray structure of 1H reveals an unprecedented central Cu12 hollow icosahedron. Six faces of this icosahedron are capped by Cu3 triangles, the whole Cu30 core being wrapped by twelve dithiophosphate ligands and the whole cluster has ideal S6 symmetry. The locations of the 18 hydrides in 1H were ascertained by a single-crystal neutron diffraction study. They are composed of three types: capping μ3-H, interstitial μ4-H (seesaw) and μ5-H ligands (square pyramidal), in good agreement with the DFT simulations. The numbers of hydrides and ligand resonances in the 1H NMR spectrum of 1H are in line with their coordination environment in the solid state, retaining the S6 symmetry in solution. Furthermore, two new Se-protected polyhydrido copper nanoclusters, [Cu30H18{Se2P(OR)2}12] ( 2H : R=iPr 3H : R=iBu) were synthesized from their sulfur relative 1H via ligand displacement reaction and their X-ray structures feature the exceptional case where both the NC shape and size are fully conserved during the course of ligand exchange. DFT and TD-DFT calculations allow understanding the bonding and optical properties of clusters 1H – 3H . In addition, the reaction of 1H with [Pd(PPh3)2Cl2] in the presence of terminal alkynes led to the formation of new bimetallic Cu−Pd alloy clusters [PdCu14H2{S2P(OnPr)2}6(C≡CR)6] ( 4 : R=Ph; 5 : R = C6H4F).  相似文献   
4.
We derive new expressions for the Rayleigh–Schrödinger series describing the perturbation of eigenvalues of quantum Hamiltonians. The method, somehow close to the so-called dimensional renormalization in quantum field theory, involves the Birkhoff decomposition of some Laurent series built up out of explicit fully non-resonant terms present in the usual expression of the Rayleigh–Schrödinger series. Our results provide new combinatorial formulae and a new way of deriving perturbation series in quantum mechanics. More generally we prove that such a decomposition provides solutions of general normal form problems in Lie algebras.  相似文献   
5.
In this article, we shall study the inviscid limit of two dimensional fluids with bounded voticity. We prove that the solution of incompressible Navier-Stokes system converges strongly in L2 to the solution of the Euler incompressible system in the case of two-dimensional fluids in the whole space.  相似文献   
6.
We define new families of noncommutative symmetric functions and quasi-symmetric functions depending on two matrices of parameters, and more generally on parameters associated with paths in a binary tree. Appropriate specializations of both matrices then give back the two-vector families of Hivert, Lascoux, and Thibon and the noncommutative Macdonald functions of Bergeron and Zabrocki.  相似文献   
7.
The electroreduction of a mixture of SO2 and CF3Br in DMF, in an undivided cell with a soluble anode (Mg or Zn) lead to salt of trifluoromethane sulfinic acid in high yield.  相似文献   
8.
Three methods have been proposed for the preparation of functionalized 1-oxo-1,2,3,4-tetrahydro-β-carboline-3 carboxylates (3) from which the “acylazide formation-Curtius rearrangement-acid catalyzed ring closure” sequence starling from hemi-ester hemi-acids (8) seemed to be quite general.  相似文献   
9.
Barium complexes ligated by bulky boryloxides [OBR2] (where R=CH(SiMe3)2, 2,4,6-iPr3-C6H2 or 2,4,6-(CF3)3-C6H2), siloxide [OSi(SiMe3)3], and/or phenoxide [O-2,6-Ph2-C6H3], have been prepared. A diversity of coordination patterns is observed in the solid state for both homoleptic and heteroleptic complexes, with coordination numbers ranging between 2 and 4. The identity of the bridging ligand in heteroleptic dimers [Ba(μ2-X1)(X2)]2 depends largely on the given pair of ligands X1 and X2. Experimentally, the propensity to fill the bridging position increases according to [OB{CH(SiMe3)2}2)]<[N(SiMe3)2]<[OSi(SiMe3)3]<[O(2,6-Ph2-C6H3)]<[OB(2,4,6-iPr3-C6H2)2]. This trend is the overall expression of 3 properties: steric constraints, electronic density and σ- and π-donating capability of the negatively charged atom, and ability to generate Ba ⋅ ⋅ ⋅ F, Ba ⋅ ⋅ ⋅ C(π) or Ba ⋅ ⋅ ⋅ H−C secondary interactions. The comparison of the structural motifs in the complexes [Ae{μ2-N(SiMe3)2}(OB{CH(SiMe3)2}2)]2 (Ae = Mg, Ca, Sr and Ba) suggest that these observations may be extended to all alkaline earths. DFT calculations highlight the largely prevailing ionic character of ligand-Ae bonding in all compounds. The ionic character of the Ae-ligand bond encourages bridging coordination, whereas the number of bridging ligands is controlled by steric factors. DFT computations also indicate that in [Ba(μ2-X1)(X2)]2 heteroleptic dimers, ligand predilection for bridging vs. terminal positions is dictated by the ability to establish secondary interactions between the metals and the ligands.  相似文献   
10.
Thirteen novel dipolar and V-shaped chromophores with pyranylidene electron-donating part, diazine electron-withdrawing part and various π-linkers were synthesized. The extent of intramolecular charge transfer, structure-property relationships and optical properties were further investigated by UV/Vis absorption, electrochemistry, and DFT calculations.  相似文献   
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