The influence of polytypic structures on the M011-->M101 solid-solid phase transition of n-C36H74: an application of the oblique infrared transmission method.

The molecular displacements on the M011→M101 phase transition of n-hexatriacontane (n-C36H74) have been investigated with an IR microscope designed for the oblique infrared transmission method. It has been clarified that two polytypic structures of the M011 modification, single-layered structure (Mon) and double-layered one (Orth II), both transform to the M101 modification of single-layered structure with their respective mechanisms. On the M011(Mon)→M101 transition, the inclination direction of molecular axis is changed by 90° through an intermediate state in which the molecular chain is set perpendicular to the basal plane of the single crystal. On the other hand, a polymorphic-polytypic composite structural change on the M011(Orth II)→M101 transition is accomplished through two kinds of molecular displacements occurring alternately along the stacking direction of molecular layers.