Investigation of the structure and interaction of cellulose triacetate I crystal using ab initio calculations

• We investigated the crystal structure of CTA I using DFT calculation.
• Dispersion correction term is effective in the calculation.
• The calculated cell parameters explain the thermal expansion of the crystal.
• AIM calculation shows the existence of CH/O interaction in the crystal of CTA I.

The crystal structure of cellulose triacetate I (CTA I) was investigated using first-principles density functional theory (DFT) calculations. The results are in good agreement with the experimental structure obtained by Sikorski et al. when performing the calculation with inclusion of the dispersion correction. However, the cell parameters calculated with inclusion of the dispersion correction are slightly smaller than those experimentally obtained, especially along the a-axis. This smaller cell parameter could be reasonably explained by considering thermal expansion effects, since optimization with the density functional calculation gives the structure without inclusion of thermal effects. The atoms-in-molecules (AIM) theory is also employed to identify and characterize interatomic interactions in the CTA I crystal. CH/O interactions sites are shown to exist in the crystal structure of CTA I. Moreover, CH/O interactions are considered the main interactions in operation to maintain the crystal structure of CTA I.

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