ABSTRACT
Theoretical treatment of the statistical properties of linear polymers (LPs), shown schematically in Figure 7.1a, have been in existence since the 1950s (Rouse, 1953), and have undergone continuous re†nement. In particular, tube theories (viz. reptation) (de Gennes, 1971; Doi and Edwards, 1986), and subsequent re†nements, like constraint release (Viovy et al., 1991) and contour length Žuctuation (Frischknecht and Milner, 2000) are some of the greatest
CONTENTS
7.1 Introduction ................................................................................................ 193 7.2 Model and Methods .................................................................................. 195
7.2.1 Model ............................................................................................... 195 7.2.2 Equilibration ................................................................................... 197 7.2.3 Primitive Path Analysis ................................................................ 198
7.3 Size ............................................................................................................... 199 7.4 Topology ...................................................................................................... 203 7.5 Dynamics .................................................................................................... 209 7.6 Free Energy ................................................................................................. 212
7.6.1 Preliminaries .................................................................................. 212 7.6.2 Implementation .............................................................................. 214 7.6.3 Discussion ....................................................................................... 218
7.7 Deviations from Theory at High Molecular Weights ........................... 226 References .............................................................................................................227
