Free volume structure of realgar α-As4S4 by positron annihilation lifetime spectroscopy

Atomic-deficient free volume structure of realgar alpha-As4S4, the low-temperature modification, of tetra-arsenic tetrasulfide polymorphs, is studied using positron annihilation lifetime spectroscopy. Eventual channels of positron annihilation in this molecular crystal are shown to be connected with low electron density entities around cage As4S4 molecules composing realgar-type structure of monoclinic P21/n space group. The overlapped spaces of bond-free solid angles around S atoms forming self-closed As4S4 molecules contribute preferentially to positron trapping modes, while a competitive influence of bound positron-electron states (positronium) stabilized in intermolecular spaces occurs also to be essential in the decomposed lifetime spectra too. (C) 2014 Elsevier Ltd. All rights reserved.