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

    2 Citations (Scopus)

    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 Sept 2022
    MoE publication typeA1 Journal article-refereed

    Keywords

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

    Fingerprint

    Dive into the research topics of 'Thermodynamic Properties of Crystalline Cellulose Allomorphs Studied with Dispersion-Corrected Density Functional Methods'. Together they form a unique fingerprint.

    Cite this