A profound analysis of Rb2[PH] and Cs2[PH] and the role of [PH]2− ions during temperature-induced solid–solid phase transitions

Abstract The temperature-induced solid–solid transformation of Rb 2 [PH] and Cs 2 [PH] is characterized from both experiment and theory. Neutron diffraction, IR-spectroscopy and ab-initio molecular dynamics simulations reveal an asymmetric shift of the lattice constants at 80 K. The molecular mechanism of the structural transformation as identified from IR-spectroscopy and ab-initio molecular dynamics simulations is closely connected to the orientation of the [PH] 2− moieties which undergo a partial order–disorder phase transition.