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For any given polymer, the weight average molecular weight (Mw) is higher than, if not equal to, the number average molecular weight (Mn). The only situation in which the weight average molecular weight and the number average molecular weight are equal is when a polymer consists only of chains with equal molecular weight. However, this never happens in a synthetic polymer, since it is difficult to control the polymerization process up to a molecular level with accuracy to a hundred percent.
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Salt particles that have dissolved in water never spontaneously come back together in solution to reform solid particles. Moreover, a gas that has expanded in a vacuum remains dispersed and never spontaneously reassembles. The unidirectional nature of these phenomena is the result of a thermodynamic state function called entropy (S). Entropy is the measure of the extent to which the energy is dispersed throughout a system, or in other words, it is proportional to the degree of disorder of a...
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Step growth polymerization involves bi or multifunctional monomers. Bifunctional monomers react to form linear step growth polymers, whereas multifunctional monomers react to form non-linear or branched polymers.
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Predicting the Mobility Increase of Coarse-Grained Polymer Models from Excess Entropy Differences.

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Coarse-graining polymer dynamics acceleration can be explained by excess entropy differences. This finding for unentangled polymers may allow for a posteriori correction of coarse-graining dynamics.

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Area of Science:

  • Polymer Physics
  • Computational Chemistry
  • Statistical Mechanics

Background:

  • Coarse-grained polymer models accelerate simulations but can alter dynamics.
  • Understanding the link between coarse-graining resolution and dynamic acceleration is crucial.

Purpose of the Study:

  • To investigate the relationship between excess entropy differences and dynamic acceleration in coarse-grained polymer models.
  • To explore the accuracy of two-body approximations and scaling of excess entropy.

Main Methods:

  • Systematic derivation of two coarse-grained models from a bead-spring unentangled polymer melt model.
  • Calculation of exact excess entropies using two-step thermodynamic integration.
  • Correlation analysis between excess entropy differences and dynamical properties.

Main Results:

  • Excess entropy differences between coarse-grained models correlated well with the logarithm of dynamical acceleration ratios.
  • The two-body approximation to excess entropy showed moderate correlation.
  • Results were consistent for unentangled polymers.

Conclusions:

  • Dynamic acceleration in coarse-grained polymer models is linked to excess entropy differences.
  • This correlation offers a potential pathway for correcting coarse-graining dynamics post-hoc.
  • The findings advance the understanding of coarse-graining methodologies in polymer science.