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Kinetics and dynamic properties of equilibrium polymers
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Image of FIG. 1.
FIG. 1.

Bounded potential (solid line) and unbounded potential (dashed line) between a pair of monomers. Each monomer can participate in at most two bounded links with two other monomers. The bonding/unbonding transition zone is also indicated. All parameters are in reduced units (see the text).

Image of FIG. 2.
FIG. 2.

Short time behavior of the distribution of first recombination times for attempt frequency (squares) and its two contributions distinguishing recombinations with the same or with new partners, indicated by dots and triangles, respectively. The dashed line (with slope ) represents the power law expected for short times. The solid line represents the long time mean-field prediction [Eq. (3)] multiplied by the transmission coefficient .

Image of FIG. 3.
FIG. 3.

Cumulative Hazard curves of recombination times for various attempt frequencies , 0.5, 1.0, and 5.0, from bottom to top. The straight line associated to the case gives an example of the linear asymptote of of slope and ordinate at origin (see the table).

Image of FIG. 4.
FIG. 4.

Time evolution of for the -jump experiment, with , starting at equilibrium at temperature and setting at the temperature . Simulation results are shown as circles and the theoretical curve by the continuous line.

Image of FIG. 5.
FIG. 5.

Mean square displacement of monomers for , 1.0, and 5.0, displayed, respectively, by thick continuous, dashed, and dotted lines. For the short time (dash-dotted line) and long time (thin dotted line) asymptotes are also drawn. Their intercept defines the crossover time . In the inset, is drawn vs on a log-log scale. The straight line (with slope ) corresponds to a power law .

Image of FIG. 6.
FIG. 6.

Simulation results of the stress-stress time correlation function for (dots), (squares), and (circles). The lines represent the theoretical curves based on Eq. (18), after fitting the amplitude (see text).


Generic image for table
Table I.

Kinetic data relative to the four scission-recombination attempt frequencies (see text for details). The fraction of effective transitions is estimated via the cumulative hazard analysis. The fraction of recombinations with a new partner is given by . is the total number of scissions taking place within the system per unit time and unit volume. All other entries are estimates of the scission rate constant as obtained by different analyses on the same BD trajectory.


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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Kinetics and dynamic properties of equilibrium polymers