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  • 1
    Electronic Resource
    Electronic Resource
    s.l. : American Chemical Society
    The @journal of physical chemistry 〈Washington, DC〉 80 (1976), S. 1544-1548 
    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 94 (1991), S. 7564-7564 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    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 92 (1990), S. 1275-1284 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Molecular dynamics calculations are reported on dense hard sphere fluids at three packing fractions (η=0.30,0.40,0.48). Attention is directed to the analysis of correlated recollisions of pairs of particles. The short time dynamics [t(approximately-equal-to)0(τc) where τc=1/collision frequency] is governed by correlated backscattering collisions as evidenced by persistence of vector time correlations. For longer times a crossover takes place from the correlated backscattering regime (or geminate recombination) to the diffusive-like regime (nongeminate recombination) in which vector correlations decay faster than scalar correlations. Recollisional events are categorized as first recollisions, second recollisions, and all recollisions. The resulting correlation functions exhibit different evolutionary time scales. Contributions to the time correlation functions (tcfs) from collision sequences involving three and four particles are also separated and analyzed.
    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 91 (1989), S. 1252-1257 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Recollision kinetic theory (RcKT) is applied to the calculation of the rotational friction coefficient of a hard nonspherical convex body in a dense fluid of hard spheres. The ratio of the rotational friction, fR , to its Enskog value, fER , is determined to be fR/fER(approximately-equal-to)1+1.06ρ* exp(5ρ*2), where ρ* is the packing fraction of the hard sphere solvent. RcKT accounts for the effect of caginglike correlated recollisions on molecular rotation. The above equation brings kinetic theory predictions of rotational friction and orientational correlation times into closer accord with experimental and molecular dynamics derived values.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 4874-4883 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The methods of classical kinetic theory for rigid nonspherical bodies are used to calculate bimolecular reaction cross sections for gas phase atom–diatom (A+BC→AB+C) reactions. The pre-collisional conditions for reaction are determined by the angle-dependent line of normals (ADLN) model whereas the post-collisional properties, such as the angular momentum and recoil energy, of the reaction products are determined by the direct interaction with product repulsion (DIPR) model. Derived cross sections are functions of the pre-collisional orientation of the diatom, the initial and final relative velocity, and the rotational angular momentum of the AB product. The hybrid, ADLN–DIPR model is applied to the analysis of the cross sections for the Ba+N2O reaction. Interpretation of the cross-section data requires both the ADLN and DIPR models and no collection of reasonable parameters in either the ADLN or the DIPR models individually can simply account for the measured cross sections.
    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 93 (1990), S. 8816-8820 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Rotational energy relaxation cross sections, σR , for nitrogen in dilute atomic gases (He, Ne, Ar, and Xe) are calculated by classical trajectory simulations for a variety of simple potentials and from the Boltzmann equation for hard convex bodies in the single impulse collision approximation. The single impulse approximation, which ignores multiple impulse (chattering) collisions, is reasonably adequate to describe linear and angular momentum relaxation, but not rotational energy relaxation. For the light noble gases, the hard body derived results together with the small chattering corrections suffice to fit σR . It is also the case that chattering collisions markedly decrease σR from the single impulse approximation value for Xe–N2 in the hard-body model. However, the value of σR experimentally measured and calculated by Kistemaker and de Vries using a soft potential is considerably less than that obtained from hard-body models including chattering. Addition of a square well attractive potential of the appropriate shape to the hard core potential leads to the desired decrease in σR with well depth in accord with both the trajectory calculations and experiments of Kistemaker and de Vries. The reasons are analyzed.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 88 (1988), S. 5035-5041 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The Mori method and the pseudo-Liouville formalism have been combined in an analysis of the translational and rotational diffusion coefficients of a dense fluid of hard bodies. Correlated recollisions, due to caging, appear naturally in this theory and their effect is to increase the translational friction on a tagged spherical molecule in a hard sphere bath and to increase the rotational friction on a hard nonspherical convex body in a hard sphere fluid. The calculated increase in friction from liquid state correlated caging corrections is in rough accord with the molecular dynamics calculation of Alder et al. on spherical systems and brings kinetic theory predictions for rotational friction coefficients in closer accord with experiment.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 88 (1988), S. 3401-3401 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Type of Medium: Electronic Resource
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  • 9
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 93 (1990), S. 4254-4265 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: In the Onsager theory for the phase transition from the isotropic fluid to the nematic liquid crystal phase, the Helmholtz free energy of a fluid of hard convex bodies (HCBs) is expressed as the sum of an entropy of a mixing-like term and an energy-like term (from the interaction of the HCBs). Whereas the Onsager theory expresses the interaction term in a virial expansion and determines the consequences of B2 alone, here we extend that treatment to incorporate B3 (with its attendant dependence on the mutual orientation of three HCBs). For HCBs (and specifically for D∞h ellipsoids) with large aspect ratios (5:1 or greater), the incorporation of B2 and B3 suffices to predict the variation of the order parameter 〈P2[cos(θ)]〉 with density in accord with the Monte Carlo (MC) results of Allen and Wilson. As the aspect ratio decreases (from 5:1) to more spherical molecules (say 3:1), virial coefficients of higher order than B3 contribute to the interaction term and their effect is represented in part by the y-expansion (or resummation) theory proposed by Barboy and Gelbart. In this y-expansion–third virial-Onsager theory, the predicted transition densities are in accord with the MC values of Frenkel and Mulder for prolate ellipsoids. Neither the y expansion nor the direct B2 and B3 theories find the phase diagram (i.e., transition density and order parameter regarded as a function of aspect ratio) to be symmetric for prolate and oblate ellipsoids. The dependence of B3 on the mutual orientation of the ellipsoids is also discussed and previous work is also addressed.
    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 91 (1989), S. 4912-4919 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A Smoluchowski equation is derived that depicts the relative diffusion of a sphere with respect to a fixed nonspherical convex body. The transport equation is expressed in terms of the surface-to-surface separation s, measured along the surface normal k. In this coordinate system, the effects of particle shape anisotropy can be subsumed by an appropriate mapping of the radius of the convex excluded volume surface onto that of an equivalent spherical system. Steric effects in diffusion-controlled reaction rates and shape anisotropy corrections to the recollision kinetic theory of rotation are analyzed in light of the chosen coordinates and the explicit Smoluchowski equation.
    Type of Medium: Electronic Resource
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