In the vapour phase and close to the liquid–vapour saturation curve, fluids made of complex molecules are expected to exhibit a thermodynamic region in which the fundamental derivative of gasdynamic G is negative. In this region, non-classical gasdynamic phenomena such as rarefaction shock waves are physically admissible, namely they obey the second law of thermodynamics and fulfil the speed-orienting condition for mechanical stability. Previous studies have demonstrated that the thermodynamic states for which rarefaction shock waves are admissible are however not limited to the G <0 region. In this paper, the conditions for admissibility of rarefaction shocks are investigated. This results in the definition of a new thermodynamic region ...