Terahertz Fingerprints of Short-Range Correlations of Disordered Atoms in Diflunisal

This work proposes a terahertz (THz) spectroscopy approach to the investigation of one of the outstanding problems in crystallographythe structure analysis of a crystal with disorder. Form I of diflunisal, in which the two ortho sites on one phenyl ring of diflunisal show occupational disorder, was used for an illustration. THz radiation interacts with the collective vibrations of correlated disorder, thus providing a promising tool to examine the symmetry of short-range correlations of disordered atoms. Through a thorough examination of the selection rule of THz vibrations in which the disordered atoms are involved to different extents, we deduced that only four short-range correlation possibilities of disorder exist and all of them display unambiguous fingerprint peaks in the 50–170 cm–1 frequency region. We finally proposed an alternating packing model in which the correlation lengths of disorder are on the nanometer scale.