Being well studied, I and II polymorphic
structures of aspirin are very suitable for testing a new method to
study mechanical properties using quantum chemical calculations. The
proposed method consists of two steps: analysis of the pairwise interaction
energies between molecules in a structure obtained by the X-ray diffraction
study with separation of strongly bound fragments and further quantum
chemical modeling of their displacement in relation to each other.
Application of this method to aspirin polymorphs I and II showed that they have layered structure and the [001] crystallographic
direction within the (100) plane is the most probable for a shear
deformation, which correlates well with the data of the nanoindentation
method. The energy barriers for the displacement in this direction
were calculated as 17.1 and 14.5 kcal/mol for polymorphs I and II, respectively. It was shown that the area of
strong repulsion between molecules belonging to the neighboring layers
can complicate shear deformation in stable crystal forms I and II of aspirin. A similar study of the latest polymorph IV showed that this structure is not layered but columnar.
The easiest shear deformations are possible for the displacement in
the [010] crystallographic direction within the (100), (−101),
and (001) planes. The low-energy barriers for these displacements
(5.4, 8.8, and 9.5 kcal/mol, respectively) and the absence of significant
repulsion along all the translation may explain the metastability
of this structure. The proposed method is a good tool to predict mechanical
properties.
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