A density-functional calculation of dynamic dipole polarizabilities of noble gas atoms

Using a very simple trial function and unperturbed electron densities calculated by a new procedure, the frequency-dependent dipole polarizability () of Ne, Ar, Kr and Xe has been calculated in the range 0 0.45 a.u., by a Karplus-Kolker-type variation-perturbation method. Results progressively worsen for larger systems so that, for Xe, (0) is only 75% of the experimental value. Probable reasons for this are discussed.     

Electronic and Spatial Structure of Piperidine and Its Substituted Derivatives from the Results of ab initio Calculations

The results of non empirical quantum-chemical calculations using the RHF/6-31G(d) and MP2/6-31G(d) methods do not agree with proposals for the axial position of the H atom on the N atom in the piperidine molecule. According to RHF/6-31G(d) calculations for the N-methylpiperidine molecule and its chloro-substituted derivatives an equatorially placed methyl group is energetically more favored than an axial. The axial C-Cl and C-H bonds in these molecules are longer than the equatorial. The ³⁵ Cl NQR frequencies for the axial Cl atoms are lower than the equatorial. The ³⁵ Cl NQR frequency of the axial chlorine atom in 2-chloro-1-methylpiperidine is anomalously low. This is chiefly due to the high population density of its p σ-orbital and this is a result of the polarization of the C-Cl bond via the N atom unshared electron pair directly through the field. The effect of a similar unshared electron pair on the parameters of the C-Cl bond in the ClCH₂NH₂ molecule has been studied by the RHF/6-31(g) method for different angles of rotation of the ClCH₂ group around the C-N bond. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 1044–1052, July, 2005.     

Electron correlation effects on the shape of the Kohn–Sham molecular orbital

Even systems in which strong electron correlation effects are present, such as the large near-degeneracy correlation in a dissociating electron pair bond exemplified by stretched H₂, are represented in the Kohn–Sham (KS) model of non-interacting electrons by a determinantal wavefunction built from the KS molecular orbitals. As a contribution to the discussion on the status and meaning of the KS orbitals we investigate, for the prototype system of H₂ at large bond distance, and also for a one-dimensional molecular model, how the electron correlation effects show up in the shape of the KS σ _g orbital. KS orbitals φ^HL and φ^FCI obtained from the correlated Heitler-London and full configuration interaction wavefunctions are compared to the orbital φ^LCAO, the traditional linear combination of atomic orbitals (LCAO) form of the (approximate) Hartree-Fock orbital. Electron correlation manifests itself in an essentially non-LCAO structure of the KS orbitals φ^HL and φ^FCI around the bond midpoint, which shows up particularly clearly in the Laplacian of the KS orbital. There are corresponding features in the kinetic energy density t _s of the KS system (a well around the bond midpoint) and in the one-electron KS potential v _s (a peak). The KS features are lacking in the Hartree-Fock orbital, in a minimal LCAO approximation as well as in the exact one. Received: 11 December 1996 / Accepted: 10 January 1997     

Radical addition reactions: factors determining the transition-state geometry

Interatomic distances in the reaction centers of the addition reactions of (i) H^· to the C=C, C=O, N≡C, and C≡C bonds, (ii) ^·CH₃ radical to the C=C, C=O, and C≡C bonds, and (iii) alkyl, aminyl, and alkoxyl radicals to olefin C=C bonds were determined using a new semiempirical method for calculating transition-state geometries of radical reactions. For all reactions of the type X^· + Y=Z → X— Y—Z^· the r ^# _X...Y distance in the transition state is a linear function of the enthalpy of reaction. Parameters of this dependence were determined for seventeen classes of radical addition reactions. The bond elongation, Δr ^# _X...Y, in the transition state decreases as the triplet repulsion, electronegativity difference between the atoms X and Y in the reaction center, and the force constant of the attacked multiple bond increase. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 894–902, April, 2005.     

Effect of boron non-stoichiometry on B-site in perovskite type structure ScBxRh3 and CeBxRh3 on charges of atoms on A-site: study by X-ray photoelectron and nuclear magnetic resonance spectroscopies

The solid solutions of ScBRh₃-ScRh₃ and CeBRh₃-CeRh₃ are synthesized by the arc melting method, where RBRh₃ and RRh₃ (R=rare earth element) have perovskite and AuCu₃ type structures, respectively. The binding energy of Sc 2p_3/2 for ScB_xRh₃ increases with the boron concentration. The Knight shift of ⁴⁵Sc observed by nuclear magnetic resonance spectroscopy decreases with increase of boron concentration. The decrement of the Knight shift corresponds the Sc 4s electron density at the Fermi level. The intensity ratio of f²: f¹: f⁰ of Ce 3d XPS spectrum changes with boron concentration of CeB_xRh₃. It is concluded that in both cases of ScB_xRh₃ and CeB_xRh₃ the charge on the atoms on A-site changes with the concentration of the atoms on B-site, where the atoms are not directly bound.     

Synthesis and Crystal Structur of (4,4''-H2bipy)[CdBr4]·H2O

The title compound (4,4'-H2bipy)[CdBr4]·H2O 1 has been synthesized via hydrothermal reaction and characterized by X-ray diffraction. The crystal belongs to monoelinic,space group P21/c with a=8.260(3), b=23.926(7), c=9.774(2) (A), β=106.777(9)°,C10H12Br4CdN2O, Mr=608.26, V=1849.4(9)(A)3, Z=4, Dc=2.185 g/cm3, S=1.005, μ(MoKα)=9.814 mm-1, F(000)=1128, R=0.0646 and wR=0.0989. The crystal structure analysis of 1reveals that the title compound features an isolated structure, based on discrete 4,4'-H2bipy moieties and lattice water molecules which are linked by hydrogen bonds together with tetrahedral cadmium atoms terminally coordinated by four bromine atoms.     

Cadmium colloids from non-aqueous solvents

Cadmium colloids have been prepared by Chemical Liquid Deposition (CLD). The metal is evaporated to yield atoms which are solvated at liquid nitrogen temperature, and upon warming, stable liquid colloids are formed with particle size ranging between 25–100 Å. Zeta potentials were calculated according to the conversion of Hunter and the Hückel equation, for ethanol and dimethyl sulphoxide. UV/VIS measurement of most of the black colloids showed absorption band around 280 nm. For comparison, we prepared CdS colloid with size 400–625 Å. The colloids are stable to oxidation in air and/or oxygen bubbling. The synthesis of colloids and films from Cd with acetone, 2-butanone, ethanol, 2-propanol, 2-methoxyethanol, DMF and DMSO is reported. Transmission Electron Microscopy (TEM) allows us to determine particle size.     

Medium-size Gaussian basis sets for hydrogen through argon

Summary Medium-sized Gaussian basis sets are reoptimized for the ground states of the atoms from hydrogen through argon. The composition of these basis sets is (4s), (5s), and (6s) for H and He, (9s5p) and (12s7p) for the atoms Li to Ne, and (12s8p) and (12s9p) for the atoms Na to Ar. Basis sets for the² P states of Li and Na, and the³ P states of Be and Mg are also constructed since they are useful in molecular calculations. In all cases, our energies are lower than those obtained previously with Gaussian basis sets of the same size.     

A chelating resin containing S, N and O atoms: Synthesis and adsorption properties for Hg(II)

A novel chelating resin containing S, N and O atoms (PSME-EDA) was synthesized by using poly(2-hydroxyethylmercaptomethylstyrene) (PSME) and diethanolamine (EDA) as materials. Its structure was characterized by elemental analysis, Fourier transform-infrared spectra (FTIR), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The adsorption of the resin for Hg²⁺ was investigated. The saturated adsorption capacity of PSME-EDA for Hg²⁺ could reach to about 1.1 mmol/g at 25 °C when the initial Hg²⁺ concentration was 0.02 mol/l. Some factors affecting the adsorption such as temperature, reaction time and ion concentration were also studied. The results showed that adsorption was controlled by liquid film diffusion. The increasing of temperature was beneficial to adsorption. The Langmuir model was better than the Freundlich model to describe the isothermal process. The values of ΔG, ΔH, and ΔS calculated at 25 °C were −7.99 kJ mol⁻¹, 22.5 kJ mol⁻¹ and 34.4 J mol⁻¹ K⁻¹, respectively. The adsorption mechanism of PSME-EDA resin for Hg(II) was confirmed by X-ray photoelectron spectroscopy (XPS).     

Average electron momenta in many-electron atoms

In many-electron atoms, the average electron momentum p represents the mean momentum of a single electron when all the electron motions are averaged. If any two electrons are considered simultaneously, however, the average momentum p splits into two different momenta, low momentum p_< and high momentum p_>. For the 102 atoms He through Lr in their ground states, the momenta p_< and p_> are systematically examined at the Hartree–Fock limit level. It is also shown that the sum p_>+p_< and the difference p_>–p_< of the two momenta constitute upper and lower bounds to the electron-pair relative momentum p₁₂=|p₁–p₂| and to the electron-pair center-of-mass momentum P=|p₁+p₂|/2. The tightness of the bounds is discussed for the 102 atoms.