Skip to Main Content
Anisotropy and temperature dependence of structural, thermodynamic, and elastic properties of crystalline cellulose Iβ: a first-principles investigationAuthor(s): ShunLi Shang; Louis G. Hector Jr.; Paul Saxe; Zi-Kui Liu; Robert J. Moon; Pablo D. Zavattieri
Source: Modelling Simul. Mater. Sci. Eng. Volume 22, 2014; 28 p.
Publication Series: Scientific Journal (JRNL)
Station: Forest Products Laboratory
Download Publication (2.0 MB)
DescriptionAnisotropy and temperature dependence of structural, thermodynamic and elastic properties of crystalline cellulose Iβ were computed with first-principles density functional theory (DFT) and a semi-empirical correction for van der Waals interactions. Specifically, we report the computed temperature variation (up to 500 K) of the monoclinic cellulose Iβ lattice parameters, constant pressure heat capacity, Cp, entropy, S, enthalpy, H, the linear thermal expansion components, ξI , and components of the isentropic and isothermal (single crystal) elastic stiffness matrices, CS ij (T ) and CT ij (T ), respectively. Thermodynamic quantities from phonon calculations computed with DFT and the supercell method provided necessary inputs to compute the temperature dependence of cellulose Iβ properties via the quasi-harmonic approach. The notable exceptions were the thermal conductivity components, λi (the prediction of which has proven to be problematic for insulators using DFT) for which the reverse, non-equilibrium molecular dynamics approach with a force field was applied. The extent to which anisotropy of Young’s modulus and Poisson’s ratio is temperature-dependent was explored in terms of the variations of each with respect to crystallographic directions and preferred planes containing specific bonding characteristics (as revealed quantitatively from phonon force constants for each atomic pair, and qualitatively from charge density difference contours). Comparisons of the predicted quantities with available experimental data revealed reasonable agreement up to 500 K. Computed properties were interpreted in terms of the cellulose Iβ structure and bonding interactions.
- We recommend that you also print this page and attach it to the printout of the article, to retain the full citation information.
- This article was written and prepared by U.S. Government employees on official time, and is therefore in the public domain.
CitationDri,; Fernando L.; Shang, ShunLi; Hector Jr., Louis G.; Saxe, Paul; Liu, Zi-Kui; Moon, Robert J.; Zavattieri, Pablo D. 2014. Anisotropy and temperature dependence of structural, thermodynamic, and elastic properties of crystalline cellulose Iβ: a first-principles investigation. Modelling Simul. Mater. Sci. Eng. Volume 22, 2014; 28 p.
Keywordscrystalline cellulose, first-principles density functional theory, thermodynamic properties, mechanical properties
- Evaluation of reactive force fields for prediction of the thermo-mechanical properties of cellulose Iâ
- Anisotropy of the elastic properties of crystalline cellulose Iß from first principles density functional theory with Van der Waals interactions
- Model lignin oligomer pyrolysis: Coupled conformational and thermodynamic analysis of β-O-4′ bond cleavage
XML: View XML