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

The phonon properties and thermodynamics of four crystalline cellulose allomorphs, I [Formula: see text] , I [Formula: see text] , II, and III [Formula: see text] , 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 ([Formula: see text]) 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 ([Formula: see text]). 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.