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  • 1
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 4042-4054 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Intramolecular reactions in entangled polymer systems are studied in the "reptation'' or "tube'' model. In the diffusion-controlled limit the reaction rates are strongly modified by the entanglement constraints and depend sensitively on the positioning of the reactive groups. For two internally positioned groups the fraction of polymers which have reacted after time t,R(t), scales as the volume explored by a group for times small compared to ts where ts is the relaxation time of the portion of polymer connecting the groups. This leads to R(t)∼t3/4 followed by R(t)∼t3/8 for t〈ts . For times larger than ts but less than the longest relaxation or reptation time τrep , R(t) scales as the distance moved by a group along its tube: R(t)∼t1/4 followed by R(t)∼t1/2. For the longest times, t〉τrep , the unreacted fraction [1−R(t)] decays exponentially with a reaction rate constant which is much less than τ −1rep. These results motivate new direct microscopic experimental tests of the reptation model.
    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 92 (1990), S. 2637-2645 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The conformation of a polymer chain subjected to periodic straining fields of arbitrary amplitude Ω and modulation frequency ω is studied in the Rouse model of polymer dynamics in the high-frequency limit ωτR(very-much-greater-than)1 where τR is the Rouse relaxation time. We specialize to the case of sinusoidal time dependence, but our results are expected to be general. We calculate the dimensionless mean square extension μ of a polymer segment containing s monomers, defined as the ratio of the mean square size to the equilibrium value. For simple shear we find μ=3+λ2f1(φ) for large segments, ωτs(very-much-greater-than)1, where τs is the segment relaxation time, λ≡Ω/ω, and f1 is a nonuniversal function of the phase, φ≡ωt, of the straining field. For small segments, ωτs(very-much-less-than)1, we find μ=3+λ2(ωτs)1/2 f2(φ) with nonuniversal f2. In extensional flow the extension along the stretching axis is derived: μ=f3(φ, λ) for ωτs(very-much-greater-than)1 and μ=1+(ωτs)1/2 f4(φ, λ) for ωτs(very-much-less-than)1 (again f3 and f4 are nonuniversal). These results are interpreted in terms of blobs of relaxation time ∼ω−1: the chain of blobs deforms affinely in the flow, but within a blob the polymer has time to relax. In the nonlinear régime (λ(approximately-greater-than)1) the blobs are strongly distorted and the polymer within a blob relaxes to an elongation well beyond its equilibrium size such that its dimensions vary linearly with number of monomers. In the case of elongational flow, the fluctuations in the velocity field entirely suppress the "yo–yo'' instability that has been conjectured to play an important role in the phenomenon of drag reduction.
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  • 3
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 88 (1988), S. 7117-7128 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: This paper analyzes diffusion controlled reactions between Brownian particles in d dimensions separated by a d−1-dimensional hyperplane. We calculate the rate coefficient k(t) defined by N(overdot)=k(t)ρAρB, where N(overdot) is the reaction rate per unit interface area, ρi is the number density of i far from the interface on the side containing i, and t is the reaction time. k(t) is expressed in terms of the particle diffusion coefficients Di and the distance of closest approach between the components before a reaction. The critical dimension dc at which reaction kinetics cross over from compact (d〈dc) to noncompact (d〉dc) behavior is reduced by the presence of an interface to dc =1 from dc =2 for reactions without an interface. Thus, for d〉1, k(t) exhibits all the characteristics of noncompact reactions. For example, k(t) has a constant long time limit k. For noncompact cases with d〉2 we find that when DA/DB(very-much-greater-than)1 the more mobile species dominates (k∝DA) while for d=2 the slow species enters logarithmically and k vanishes in the limit DB →0 [k∝DA/ln(DA/DB)]. The crossover case d=dc =1 is very different and exhibits some features of compact behavior; e.g., k(t) is quenched logarithmically at long times. In this case we find, as in the d=2 noncompact case, that k(t) vanishes in the limit DB/DA→0. This effect is entirely absent for reactions without an interface and results from the rate being limited by diffusion of the slow species to the interface.
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  • 4
    Electronic Resource
    Electronic Resource
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 772-780 
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: We present a numerical study of bulk-mediated effective surface diffusion at liquid surfaces where surface-active molecules adsorb and desorb on experimental time scales. Adsorbed molecules execute Lévy walks on the interface, each step entailing desorption followed by bulk diffusion and readsorption elsewhere. Our results confirm the predicted anomalous scaling of surface displacement r at times before particles are finally lost to the bulk. Moments grow as 〈rq〉∼tζ(q), where ζ(q)=q for q〈1, ζ(q)=(q+1)/2 for q(approximately-greater-than)1. We have also confirmed that the "speed'' c which characterizes the q〈1 behavior, r≈ct, is universally related to other observables: c=D/h where D and h are, respectively, the bulk diffusivity and the slope of the equilibrium adsorption isotherm.
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