Thermodynamic Properties of Crystalline Cellulose Allomorphs Studied with Dispersion-Corrected Density Functional Methods

Divya Srivastava, Jouni Ahopelto, Antti J. Karttunen (Corresponding Author)

Research output: Contribution to journalArticleScientificpeer-review

Abstract

The phonon properties and thermodynamics of four crystalline cellulose allomorphs, Iα, Iβ, II, and III1, have been investigated using dispersion-corrected density functional theory (DFT). In line with experimental findings, the free energy differences between the studied cellulose allomorphs are small, less than 1 kJ/mol per atom. The calculated specific heat at constant volume (Cv) has been compared with the available experimental data in the temperature range 10-300 K. Quasiharmonic approximation has been employed to study thermodynamics and specific heat at constant pressure (Cp). For the studied temperature range of 10-400 K, the specific heat of all cellulose allomorphs shows very similar behavior. The calculated and experimental specific heat agree well at low temperatures below 100 K, but the deviation between theory and experiment increases with temperature. This may be due to increasing phonon anharmonicity as the temperature increases.

Original languageEnglish
Article number6240
JournalMolecules
Volume27
Issue number19
DOIs
Publication statusPublished - 22 Sep 2022
MoE publication typeA1 Journal article-refereed

Keywords

  • cellulose
  • density functional theory
  • phonon properties
  • quantum chemical calculations
  • quasiharmonic approximation
  • thermodynamics

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