62 research outputs found
Stretching Semiflexible Polymer Chains: Evidence for the Importance of Excluded Volume Effects from Monte Carlo Simulation
Semiflexible macromolecules in dilute solution under very good solvent
conditions are modeled by self-avoiding walks on the simple cubic lattice
( dimensions) and square lattice ( dimensions), varying chain
stiffness by an energy penalty for chain bending. In the absence
of excluded volume interactions, the persistence length of the
polymers would then simply be with , the bond length being the lattice spacing,
and is the thermal energy. Using Monte Carlo simulations applying the
pruned-enriched Rosenbluth method (PERM), both and the chain length
are varied over a wide range ), and
also a stretching force is applied to one chain end (fixing the other end
at the origin). In the absence of this force, in a single crossover from
rod-like behavior (for contour lengths less than ) to swollen coils
occurs, invalidating the Kratky-Porod model, while in a double crossover
occurs, from rods to Gaussian coils (as implied by the Kratky-Porod model) and
then to coils that are swollen due to the excluded volume interaction. If the
stretching force is applied, excluded volume interactions matter for the force
versus extension relation irrespective of chain stiffness in , while
theories based on the Kratky-Porod model are found to work in for stiff
chains in an intermediate regime of chain extensions. While for in
this model a persistence length can be estimated from the initial decay of
bond-orientational correlations, it is argued that this is not possible for
more complex wormlike chains (e.g. bottle-brush polymers). Consequences for the
proper interpretation of experiments are briefly discussed.Comment: 23 pages, 17 figures, 2 tables, to be published in J. Chem. Phys.
(2011
A Quantitative Theory of Mechanical Unfolding of a Homopolymer Globule
We propose the quantitative mean-field theory of mechanical unfolding of a
globule formed by long flexible homopolymer chain collapsed in poor solvent and
subjected to extensional deformation. We demonstrate that depending on the
degree of polymerization and solvent quality (quantified by the Flory-Huggins
parameter) the mechanical unfolding of the collapsed chain may either
occur continuously (by passing a sequence of uniformly elongated
configurations) or involves intra-molecular micro-phase coexistence of a
collapsed and a stretched segment followed by an abrupt unraveling transition.
The force-extension curves are obtained and quantitatively compared to our
recent results of numerical self-consistent field (SCF) simulations. The phase
diagrams for extended homopolymer chains in poor solvent comprising one- and
two-phase regions are calculated for different chain length or/and solvent
quality.Comment: 24 pages, 18 figure
Theory of the spin Hall effect, and its inverse, in a ferromagnetic metal near the Curie temperature
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