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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 93 (1989), S. 5328-5330 
    Source: ACS Legacy Archives
    Topics: Chemistry and Pharmacology , Physics
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 695-702 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Forces between planar surfaces immersed in a polymer solution are compared with those of the pure solvent in order to establish the effect of adding polymer. We use an off-lattice model consisting of hard-sphere polymers in a hard sphere (athermal solvent). The model is analyzed using a recently introduced density-functional theory. Due to the typically high density of liquids, the forces in both solution and solvent are oscillatory, leading to a more complicated picture than the classical description of polymer depletion forces. Rather than a well-defined attractive depletion regime in the surface forces, the effect of polymers is better described as a damping of the oscillatory force in the pure solvent. It is only when one goes to low (solvent and polymer) density that an attractive depletion regime can be identified.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 95 (1991), S. 5318-5326 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Electrostatic interactions in and among reverse micelles in the microemulsion are studied by the grand canonical ensemble Monte Carlo simulation (GCEMC) and by the linear response/Poisson–Boltzmann approximation (LPB). The latter theory is found to reproduce the ion-correlation effects among the micelles seen in the earlier canonical Monte Carlo approach. The open ensemble simulation and the Poisson–Boltzmann (PB) equation are used to study solubilization of simple electrolyte in the microemulsion. In systems with monovalent ions, the PB approximation agrees well with the simulation. Since individual ions are allowed to enter or leave the micelle in our GCEMC simulation, the deviations from the electroneutrality of the droplets are also studied. A good agreement with the LPB theory and with the simple charge fluctuation models considering only the Born solvation energy of charged droplets is observed. For large reverse micelles, the LPB theory and the continuum approach of Eicke and co-workers [J. Phys. Chem. 93, 314 (1989)] proved satisfactory while only the discrete model of Hall [J. Phys. Chem. 94, 429 (1990)] agrees with the simulation for small droplets. The GCEMC results lend support to recent interpretations of electric conductivity of microemulsions. The intermicellar forces due to the correlated charge fluctuation on adjacent droplets are discussed. An approximate expression for the charge fluctuation contribution to the long-ranged pair potential among large droplets with the radius Rm of the form w(r)/kT(approximately-equal-to)−(1/2)(Rm/r)2 is derived.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 92 (1990), S. 1915-1922 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: In the Poisson–Boltzmann theory of macroion screening in electrolyte solutions the chief simplifying assumption is the neglect of correlations within the ionic atmosphere. Using a generalized van der Waals density functional analysis incorporating ion–ion correlation in a local approximation we obtain a simple correlation corrected Poisson–Boltzmann theory. For point charges in the salt free case, this local correlation approximation leads to asymptotic instability (a "structuring catastrophe'') though the correction is well behaved to low orders in perturbation theory. Results in zeroth order and in a zeroth order field approximation are compared with an extended series of Monte Carlo simulations within a cell model (and a planar electrode model). An excellent agreement is found over a wide range of coupling strengths.
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 91 (1989), S. 7612-7620 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The photofragment kinetic energy spectrum of Ar+3 has been recorded in a crossed-beam apparatus at 532 nm; the only photofragment product observed is Ar+. For the purposes of analysis, a spectrum for the photofragmentation of Ar+2 was recorded under similar experimental conditions. In each case, the ions were prepared by the electron impact ionization of a neutral argon cluster beam. The Ar+3 spectrum consists of two quite distinct features, a high-energy component which closely resembles the result observed for Ar+2, and a second, low-energy feature, which is peculiar to Ar+3 alone. The two high-energy wings appear to arise from a very rapid dissociation process where approximately 70% of the excess energy appears as Ar+ kinetic energy. A computer simulation of this region of the spectrum gives an anisotropy parameter, β, of 1.1±0.2. The low-energy, component to the spectrum arises from a two-step dissociation process, in which a weakly bound atom carries away a relatively large fraction of the available excess energy to leave a quasibound dimer ion. The energetics associated with this latter process can be accounted for using a partitioning scheme proposed by Baer et al. [J. Chem. Phys. 76, 5917 (1982)]. A computer simulation of the low-energy component gives β(approximately-equal-to)0.0. A detailed discussion of the results in terms of electronic structure, photofragmentation dynamics, and allowed electronic transitions, concludes that Ar+3 takes the form of a stable dimer ion and a weakly bound atom, and that it is most probably nonlinear.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 4525-4531 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: An integral equation theory is developed for nonuniform polymer fluids. It is based on an exact formulation of the density functional theory for polymers, which is essentially identical in form to the popular self-consistent-field approximations. A nonuniform site–site Ornstein–Zernike equation is obtained. As well, the Triezenberg–Zwanzig–Wertheim–Lovett– Mou–Buff equations are generalized to polymer fluids. The Percus–Yevick and mean spherical approximations are suggested as plausible closures to these equations.
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 3666-3677 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Argon dimer ions have been generated via three different techniques: (1) autoionization; (2) vertical ionization of neutral Ar2; (3) ionization and subsequent fragmentation of argon cluster ions. In experiments (2) and (3) the dimers and clusters are formed via the adiabatic expansion of argon in a supersonic beam. In each case Ar+2 ions have been mass selected and subjected to single-photon infrared excitation (912–1094 cm−1) using a line-tunable carbon dioxide laser in a crossed-beam arrangement. Only those Ar+2 ions with internal energies within 1000 cm−1 of a dissociation limit yield Ar+ photofragments, the kinetic energy spread of which has been measured using an electrostatic analyzer. The photofragment kinetic energy spectra of dimer ions formed by autoionization do not exhibit any dependence on the angle of laser polarization; it is proposed that such behavior is due to the presence of a high thermal rotational temperature (500 K). In contrast, the corresponding spectra of Ar+2 formed via vertical ionization, exhibit two quite distinct features, one of which shows a strong dependence on laser polarization angle. Calculations show that the latter behavior is most probably due to photodissociation out of an excited spin–orbit state of Ar+2. A very pronounced increase in Ar+2 infrared photodissociation signal is observed as a function of increasing nozzle stagnation pressure. To account for such behavior it is proposed that, following ionization, argon cluster ions fragment to give dimer ions in excited vibrational/rotational levels both in the electronic ground and an excited spin–orbit state.
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 376-383 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Metastable Ar+2 (Ar+2 →Ar++Ar) has been observed in a double-focusing mass spectrometer from ions created by 70 eV electron bombardment of an Ar cluster beam. New ground and excited state potential energy curves have been calculated for Ar+2, and these have been used to show that metastability is due to radiative decay from the II(1/2)u state of the ion. It is shown that vertical (FC) ionization from neutral Ar2, with a vibrational temperature of approximately 30 K, results in a significant fraction of the ions occupying the II(1/2)u state. Detailed pressure dependent measurements show that collision-induced dissociation does not contribute to the observed Ar+ signal. The mean kinetic energy released to the Ar+ has been measured as 44 cm−1 in the center-of-mass frame, and calculations show that this value is consistent with the proposed mechanism.
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 90 (1989), S. 5657-5663 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The recently developed generalized van der Waals (GvdW) theory, a free energy density functional theory based on cell theory and van der Waals approximations, is here applied to the prediction of hard sphere oscillatory structures at a hard wall, between two hard walls, and around a hard sphere. Three different functional forms of the crucial free volume factor are compared. The results confirm that the fine-grained GvdW theory containing a nonlocal entropy functional yields structures reproducing packing oscillations not only qualitatively but to quantitative accuracy. The error depends on the choice of free volume factor and can be made small except at high density where the range and magnitude of oscillations are overestimated. Evidence of early onset of a hard sphere freezing transition is seen.
    Type of Medium: Electronic Resource
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  • 10
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 89 (1988), S. 5140-5144 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We investigate a recent theory for macroionic dispersions due to Sogami and Ise, which advocates the use of the Gibbs free energy in place of the usual Helmholtz description of the counterion thermodynamics. Employing the Poisson–Boltzmann approximation, their model predicts an effective electrostatic interaction between macroions which is attractive for spheres, in contradiction to the much used DLVO potential. By applying their analysis to a planar geometry of charged walls with only counterions we make explicit the consequences of their assumption that the thermodynamic potentials are first-order homogeneous functions of the extensive parameters in the system. This is no longer the case of the nonuniform systems inherent in the calculation of effective potentials.
    Type of Medium: Electronic Resource
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