High pressure and low temperature X-ray crystallography: the crystal structure of the molecular charge transfer salt α'- (bis(ethylenedithio)-tetrathiafulvalene) 2 AuBr 2

Abstract

An X-ray diffraction technique is described that allows determination of crystal structure and the variation of lattice parameters of single crystals as a function of hydrostatic pressure up to 14 kbar and of temperature from 300 K to 12 K. As an example of the technique results are presented on the molecular charge transfer salt α'-(BEDT TTF )2 AuBr 2 (BEDT-TTF = bis(ethylenedithio)-tetrathiafulvalene) to elucidate the nature of a structural phase transition which occurs at 250 K at ambient pressure and 7 kbar at 300 K. The transition, of second order, is characterized by the appearance of ½b* superlattice reflections at high pressure or low temperature but without any drastic change in the basic crystal structure. The isobaric thermal expansions and the isothermal compressibilities are anisotropic, being larger along a than along b and c , though of different magnitudes and directional properties, i. e. the effect of applying pressure at ambient temperature is not equivalent to lowering the temperature at ambient pressure. Transfer integral calculations show that marked dimerization along the stacking axis, already present at 300 K, is related to electronic localization.