It is shown that Monte-Carlo (MC) simulations of the elastic behaviour of c
hains in networks using realistic rotational-isomeric-state (RIS) chain mod
els are able to reproduce experimentally observed deviations from Gaussian
network behaviour in uniaxial extension and also to interpret, quantitative
ly, stress-optical properties. In stress-strain behaviour, an increase in t
he proportion of fully extended chains with increasing macroscopic strain g
ives rise to a steady decrease in the rate of change of the Helmholtz energ
y of a network, causing a reduction in network modulus at moderate macrosco
pic strains. There is no need to invoke a transition from affine to phantom
chain behaviour as deformation increases. To evaluate stress-optical prope
rties, the average orientation of segments with respect to the deformation
axis is calculated, taking into account the interdependence of segment orie
ntation and chain orientation as chains become more extended and aligned un
der uniaxial stress. The MC method gives, in agreement with experiment, val
ues of stress-optical coefficient that are dependent upon both deformation
ratio and network-chain length. The method highlights serious shortcomings
in the classical Gaussian model of stress-optical behaviour. Applications o
f the simulation methods to the quantitative modelling of the stress-strain
behaviour of poly(dimethyl siloxane) networks and the stress-optical behav
iour of polyethylene networks are described.