Polymers in dilute solution undergo a phase transition known as the
coil-globule transition (see figure 20). At low temperatures
(or in a poor solvent) the attractive interactions between monomers pull the polymer into
a dense ball-like configuration or ``globule''. At high temperatures (or in a good
solvent) the interactions are mediated by the solvent molecules, and the typical
configurations are open coils. At a specific temperature, the -point, the polymers
undergo a phase transition (much like when water boils into vapour).
These phases (coil and globule) are characterised by the asymptotic behaviour of the
average size26 of a polymer containing monomers. If we consider the radius of
gyration,
, of a polymer (which is the average distance of a monomer from the
polymer's centre of mass), then the average radius of gyration27 of polymers with
monomers is
expected to behave as
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(9) |
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Consider a linear polymer (each monomer is connected to only two others). In a real
polymer the monomers occupy positions in continuous space (
), and the bonds
between them are constrained to have only certain angles (depending upon the nature of the
monomers). We can simplify this situation by embedding the polymer into discrete space
(
), requiring that the monomers exist at integer coordinates only a single
lattice spacing apart. Since the monomers cannot occupy the same space, the polymer
embedded into discrete space is in fact a self-avoiding walk. To account for interactions
between monomers, one can study the number of nearest-neighbour contacts (the number of
points at which the walk passes within one lattice spacing of itself); by favouring or
disfavouring these contacts one can study attractive and repulsive interactions -- see
figure 21. Lattice trees and bond animals can be used to model polymers with
more complicated topologies.
The self-avoiding walk model was introduced by Orr [35] to explore the geometric
properties of linear polymers in a good solvent. At first glance it appears as though this
model is far too simple to have any hope of modelling such a complex situation, however
the phenomenon of universality tells us many quantities are not dependent on the
specific details of the system, rather they are determined only by its
universality class. The universality class is determined by the very general
properties of the system, such as its dimension, and not by the very specific details
(such as the type of lattice). All systems (real or mathematical) within the same
universality class share the same dominant asymptotic behaviour close to a phase
transition -- and so any member of the universality class can be used to determine this
behaviour. For example, the critical exponent, , in any given phase is expected to be
the same for all linear polymers in three dimensions, regardless of precise details of the
system --
for SAWs is exactly the same as
for almost any 28 linear polymer! On the other
hand, other quantities such as the exact location of the
-point are not universal,
and can only be determined by experiment.