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Polymer in a Good Solvent

J. Baschnagel, J. P. Wittmer, and H. Meyer

Framework: A conguration of the chain may be specied by the positions of the monomers. Thermodynamic properties are calculated by averaging an observable A over all configurations.

We assume that U(x) can be split into two parts:

The first term U0 depends on the chemical nature of the polymer. It comprises the potentials of the bond length , the bond angle , the torsional angle , etc.

These potentials lead to correlations between the bond vectors bi and bj.

Typically, the correlations are of short range: they only extend up to some bond vector bj=i+imax with imax << N.

Although distant monomers along the backbone of the chain are thus orientationally decorrelated, they can still come close in space.

The resulting interaction is longrange along the chain backbone and is accounted for by the second term U1. (U1 depends strongly on the quality of the solvent)

In good solvents the monomers effectively repel one another (they want to be surrounded by solvent molecules), whereas they attract each other if the solvent cannot dissolve the polymer (bad solvent).

Due to its long-range character, one intuitively expects U1 to influence the large-scale behavior of the chain more strongly than U0.

A possible test of this idea is to estimate how the size of a chain scales with N. Common measures of the chain size are the meansquare end-to-end distance or the radius of gyration.

Let bi denote the unit vector associated with the bond bi of fixed length l0

Apparently, the large-scale behavior of Re depends on the range of orientational correlations between bond vectors.

Two cases may be distinguished:

Of course, the finite-range correlations, assumed for U0 are also of short range. Thus, provided U1 = 0, the end-to-end distance of a (long) chain is given by The microscopic degrees of freedom, , , ,determine the prefactor, the effective bond length b, but not the scaling with N.

Therefore, if we are interested in studying large-scale properties, we can replace a chemically realistic model by a much simpler coarsegrained model., which is microscopically unrealistic, but correctly reproduces the large-N behavior.

An example for such a coarse-grained model is a .bead-spring model., where N effective monomers (.beads.) are connected by harmonic springs of average length b.

Two cases may be distinguished:

Thus, long-range correlations lead to a swelling of the chain size with respect to a pure random walk. Such long-range correlations are embodied in the potential U1.

For a polymer in a good solvent a swelling of the chain dimension is physically reasonable. As soon as two (distant) monomers come close in space, they repel each other.

On the level of the coarse-grained bead-spring model we can incorporate this repulsive interaction by writing U1 as

Conclusion:

When focusing on the large-scale properties of linear polymers with some flexibility and predominantly repulsive interactions we may forego a microscopic description in favor of a coarse-grained model.