β-D-核糖（ RI）与一价、二价金属离子相互作用的理论研究

在HF和MP2水平用全电子(AE)和相对论有效芯势(RECP)方法研究了Ⅰa、Ⅰb、Ⅱa和Ⅱb族金属离子与β D 核糖(RI)的相互作用. 结果表明, RECP能可靠地用于重金属离子;二价金属离子(M2＋)比一价金属离子(M＋)更易使β D 核糖(RI)变形;二价金属离子络合物(RI M2＋)比一价金属离子络合物(RI M＋)稳定. 电荷布居分析的结果支持上述结论.     

The Role of Binary and Many-centre Molecular Interactions in Spin Crossover in the Solid State. Part II. Non-ideality Parameters Defined via Binary Molecular Potentials

Summary. Parameters of the formalism [1–6] describing spin crossover in the solid state have been defined via molecular potentials in model systems of neutral and ionic complexes. In the first instance Lennard-Jones and electric dipole–dipole potentials have been used whereas in ionic systems Lennard-Jones and electric point-charge potentials have been used. Electric dipole–dipole interaction of neutral complexes brings about a positive excess energy controlled by the difference of electric dipole moments of HS and LS molecules. Differences of the order of Δμ = 1–2 D cause an abrupt spin crossover in systems with T_1/2 = 100–150 K. Magnetic coupling contributes both to the excess energy and excess entropy, however the overall effect is equivalent to a modest positive excess energy. Ionic systems in the absence of specific interactions are characterised by very small excess energies corresponding to practically linear van’t Hoff plots. Detectable positive and negative excess energies in these systems may arise from interactions of ligands belonging to neighbouring complexes. The HOMO–LUMO overlap in HS–LS pairs can bring about a nontrivial variation of the shape of transition curves. Examples of regression analysis of experimental transition curves in terms of molecular potentials are given.     

Critical Points in a Crystal and Procrystal

The critical points in the model electron density distributions of LiF, NaF, NaCl, and MgO crystals, constructed from accurate X-ray diffraction data, are determined. For LiF and MgO they are compared with those obtained from a Hartree–Fock electron density calculation. Both experiment and theory show the same type of critical points on the bond lines. The topological features in areas between structural units, where the electron density is low and near-uniform, turn out to be model dependent and cannot be established well with the data available. Topological analysis of procrystals (hypothetical systems consisting of spherical atoms or ions placed on the same sites as atoms in real crystal) show that (3, –1) critical points, usually connected with bonding interaction, are observed on interatomic lines in these nonbonded systems as well.     

Toward deformation densities for intramolecular interactions without radical reference states using the fragment,atom, localized,delocalized, and interatomic (FALDI) charge density decomposition scheme

A novel approach for calculating deformation densities is presented, which enables to calculate the deformation density resulting from a change between two chemical states, typically conformers, without the need for radical fragments. The Fragment, Atom, Localized, Delocalized, and Interatomic (FALDI) charge density decomposition scheme is introduced, which is applicable to static electron densities (FALDI‐ED), conformational deformation densities (FALDI‐DD) as well as orthodox fragment‐based deformation densities. The formation of an intramolecular NH⋅⋅⋅N interaction in protonated ethylene diamine is used as a case study where the FALDI‐based conformational deformation densities (with atomic or fragment resolution) are compared with an orthodox EDA‐based approach. Atomic and fragment deformation densities revealed in real‐space details that (i) pointed at the origin of density changes associated with the intramolecular H‐bond formation and (ii) fully support the IUPAC H‐bond representation. The FALDI scheme is equally applicable to intra‐ and intermolecular interactions. © 2017 Wiley Periodicals, Inc.     

A layer potential analysis for transmission problems for Brinkman‐type systems in Lipschitz domains in

The aim of this paper is to establish a well‐posedness result for a boundary value problem of transmission‐type for the standard and generalized Brinkman systems in two Lipschitz domains in , the former being bounded, and the latter, its complement in . As a first step, we establish a well‐posedness result for a transmission problem for the standard Brinkman systems on complementary Lipschitz domains in by making use of the Potential theory developed for such a system. As a second step, we prove our desired result (in L²‐based Sobolev spaces) by using a method based on Fredholm operator theory and the well‐posedness result from the previous step.     

Spin polarisation in dual catalysts for the oxygen evolution and reduction reactions

Strongly correlated catalysts can be understood from precise quantum approximations. Incorporating properly electronic correlations thus let’s define Spin rules in catalysis, opening a new door towards optimum compositions for the most important reactions for a sustainable future.     

Influence of metal ion on chelate–aryl stacking interactions

CCSD(T)/CBS and DFT methods are employed to study the stacking interactions of acetylacetonate‐type (acac‐type) chelates of nickel, palladium, and platinum with benzene. The strongest chelate–aryl stacking interactions are formed by nickel and palladium chelate, with interaction energies of −5.75 kcal mol⁻¹ and −5.73 kcal mol⁻¹, while the interaction of platinum chelate is weaker, with interaction energy of −5.36 kcal mol⁻¹. These interaction energies are significantly stronger than stacking of two benzenes, −2.73 kcal mol⁻¹. The strongest nickel and palladium chelate–aryl interactions are with benzene center above the metal area, while the strongest platinum chelate–aryl interaction is with the benzene center above the C2 atom of the acac‐type chelate ring. These preferences arise from very different electrostatic potentials above the metal ions, ranging from very positive above nickel to slightly negative above platinum. While the differences in electrostatic potentials above metal atoms cause different geometries with the most stable interaction among the three metals, the dispersion (correlation energy) component is the largest contribution to the total interaction energy for all three metals.