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  • 1
    ISSN: 1572-8927
    Keywords: Activity coefficients ; emf ; zinc chloride ; water activity ; Pitzer's equations ; solvation cosphere structure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The standard potential of the Zn−Hg (sat)/ZnCl2(M)/AgCl/Ag cell was determined at 25°C using several extrapolation procedures and the value 0.9843 V is proposed for E°. The emf of the Zn−Hg (sat)/ZnCl2(M), salt (M)/AgCl/Ag cell [salt=NaClO4, LiClO4, Mg(ClO4)2, Mg(NO3)2] have been measured at different concentrations of salt. From these data, the mean ionic activity coefficients of ZnCl2 are determined and their variations explained with the aid of Pitzer's treatment. It seems necessary to take into account structure in the ionic cospheres in order to explain the observed variations.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1089-7623
    Source: AIP Digital Archive
    Topics: Physics , Electrical Engineering, Measurement and Control Technology
    Notes: The design of two small, compact and portable cells for EXAFS measurements of liquids is presented. One of the cells has been optimized for transmission measurements and the other for fluorescence. The sample chamber of both cells has been designed metal free to avoid corrosion by acids or bases. Materials and construction of the cell are such that their cost is quite low. The cells have been tested by recording EXAFS spectra of ionic aqueous solutions.
    Type of Medium: Electronic Resource
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  • 3
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The simplest representation of monoatomic cations in aqueous solutions by means of a sphere with a radius chosen on the basis of a well-defined property (that of the bare ion or its hydrate) is reexamined considering classical molecular dynamics simulations. Two charged sphere–water interaction potentials were employed to mimic the bare and hydrated cation in a sample of 512 water molecules. Short-range interactions of trivalent cations were described by Lennard-Jones potentials which were fitted from ab initio calculations. Five statistically independent runs of 150 ps for each of the trivalent spheres in water were carried out in the microcanonical ensemble. A comparison of structural and dynamical properties of these simple ion models in solution with those of a system containing the Cr3+ hydrate ([Cr(H2O)6]3+) is made to get insight into the size and shape definition of simple ions in water, especially those that are highly charged. Advantages and shortcomings of using simple spherical approaches are discussed on the basis of reference calculations performed with a more rigorous hydrated ion model [J. Phys. Chem. B 102, 3272 (1998)]. The importance of nonspherical shape for the hydrate of highly charged ions is stressed and it is paradoxically shown that when spherical shape is retained, the big sphere representing the hydrate leads to results of ionic solution worse than those obtained with the small sphere. A low-cost method to generate hydrated ion–water interaction potentials taking into account the shape of the ionic aggregate is proposed. © 1999 American Institute of Physics.
    Type of Medium: Electronic Resource
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  • 4
    ISSN: 0894-3230
    Keywords: Organic Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Notes: The influence of solvation on the Z - E isomerization process of three representative molecules of simple push-pull ethylenes [H2N(H)C1=C2(H)R = NO2, COH and CN] derived from aminoethylene was investigated by means of RHF-SCF ab initio calculations at the 3-21 + G level. Solute-solvent interactions were modelled by a cavity model. The shape of the cavity is based on electronic isodensity surfaces. By using an ellipsoidal cavity very close to the isodensity surface, the perturbation due to the solvent takes an analytical form which is incorporated into the Hartree-Fock equations and leads to efficient quantum chemical computations. The polarization of the solutes under the influence of the solvent is noticeable and was analysed in detail. Similarly, the barriers to internal rotations are substantially modified by the solvent: the barrier around the C=C double bond is appreciably decreased in the thermal mechanism whereas its lowering is less important in the anionic mechanism; in contrast, the barrier around the C-1—N bond is slightly increased. The variation of the barriers with the nature of the acceptor group is fairly well reproduced by the computations. The electronic structure of the push-pull ethylene molecules and the modifications of this structure under the influence of the solvent are analysed in detail.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 5
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: This work examines the possibility of finding an electron-hole and an electron-pair simultaneously in a π-system substituted by an electron-donating (NH2) and/or electron-withdrawing (NO2) group. The contributions of various ionic [(+), ( ↑ ↓ )] structures are calculated from ab initio SCF-CI wave functions, using a recently developed general multielectron population analysis. The molecules studied are two monosubstituted ethylenes, aminoethylene and nitroethylene, and a disubstituted ethylene, the 2-nitroethenamine (push-pull ethylene) in its two configurational forms. The influence of the NH2 and/or NO2 group in delocalization and ionic (vs. covalent) character of the C=C double bond are investigated, along with examining the experimental chemist formalism of electron-pair “displacements” in several resonance structures. Analysis of mutual dependence of an electron-hole and an electron-pair, at short and long distances, leads to the conclusion that a push-pull π-system can stimulate the simultaneous existence of an electronhole and an electron-pair even for nonvicinal positions. The relationship between the electronpair distributions and contributions of the corresponding structures are also examined; the effects of electronic correlation are analyzed as well. © 1992 John Wiley & Sons, Inc.
    Additional Material: 7 Tab.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Quantum Chemistry 52 (1994), S. 1127-1144 
    ISSN: 0020-7608
    Keywords: Computational Chemistry and Molecular Modeling ; Atomic, Molecular and Optical Physics
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A method to perform a polyelectron population analysis of correlated molecular orbital wave functions on the basis of natural atomic orbitals (NAOs), as given by Weinhold, is presented. The method allows calculations of the probabilities of finding various types of electronic events occuring in some target AO positions, including the contributions of ionic and covalent resonance structures. This method is general and neither the theory nor the developed algorithm limit the number of electrons and holes that can be considered. Thus, the analyzed MO wave function can be a usual CI or a MCSCF one, and apart from Weinhold's NAOs. any other type of orthogonal AOs can be used as analyzers, provided that these AOs are linear combinations of the SCF-AOs. Numerical applications are given for ethylene, formaldehyde, butadiene, and acroleine, by adopting various AO basis-set levels (STO-4G, 4-31G, and 6-31G) and by analyzing correlated wave functions (CISD). Improvements in the polyelectron populations when increasing the quality of AO basis sets and the corresponding valence NAOs are revealed by several examples. Furthermore, it is shown that the electroegativity of oxygen in acroleine only has an effect on contributions of ionic and covalent resonance structures, but not on delocalization of the double bonds. 1993 John Wiley & Sons, Inc.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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