Local structure of liquid Rb–Se mixtures near the miscibility gap

In the liquid Rb–Se mixture there exists a liquid–liquid phase separation (miscibility gap) in the Se-rich concentration region. In order to study how the local structure is associated with the occurrence of the miscibility gap, EXAFS and neutron diffraction measurements for liquid Se, Rb₁₀Se₉₀, Rb₁₅Se₈₅ and Rb₂₀Se₈₀ mixtures have been carried out. The results reveal that the interaction between Rb and Se atoms is very weak and the liquid mixtures are composed of short Se chain-molecules of which chain ends are terminated by Rb atoms. We have carried out detailed structural modeling studies using reverse Monte Carlo simulation. It is found that the chain-like or ring-like Se segments are separated by voids. The Rb atoms adsorbed to Se chain ends segregate in the void and the shortened Se chain-molecules link up with each other when one approaches the miscibility gap.