Anisotropy and temperature dependence of structural, thermodynamic, and elastic properties of crystalline cellulose Iβ: A first-principles investigation

Fernando L. Dri, Shun Li Shang, Louis G. Hector, Paul Saxe, Zi Kui Liu, Robert J. Moon, Pablo D. Zavattieri

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Abstract

Anisotropy 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, CijS (T) and CijT (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.

Original languageEnglish (US)
Article number085012
JournalModelling and Simulation in Materials Science and Engineering
Volume22
Issue number8
DOIs
StatePublished - Dec 1 2014

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Thermodynamic Properties
Cellulose
Elastic Properties
First-principles
Temperature Dependence
cellulose
Structural Properties
Anisotropy
elastic properties
thermodynamic properties
Density Functional
Thermodynamics
Crystalline materials
Density functional theory
temperature dependence
anisotropy
Phonon
density functional theory
Non-equilibrium Molecular Dynamics
stiffness matrix

All Science Journal Classification (ASJC) codes

  • Modeling and Simulation
  • Materials Science(all)
  • Condensed Matter Physics
  • Mechanics of Materials
  • Computer Science Applications

Cite this

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title = "Anisotropy and temperature dependence of structural, thermodynamic, and elastic properties of crystalline cellulose Iβ: A first-principles investigation",
abstract = "Anisotropy 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, CijS (T) and CijT (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.",
author = "Dri, {Fernando L.} and Shang, {Shun Li} and Hector, {Louis G.} and Paul Saxe and Liu, {Zi Kui} and Moon, {Robert J.} and Zavattieri, {Pablo D.}",
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Anisotropy and temperature dependence of structural, thermodynamic, and elastic properties of crystalline cellulose Iβ : A first-principles investigation. / Dri, Fernando L.; Shang, Shun Li; Hector, Louis G.; Saxe, Paul; Liu, Zi Kui; Moon, Robert J.; Zavattieri, Pablo D.

In: Modelling and Simulation in Materials Science and Engineering, Vol. 22, No. 8, 085012, 01.12.2014.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Anisotropy and temperature dependence of structural, thermodynamic, and elastic properties of crystalline cellulose Iβ

T2 - A first-principles investigation

AU - Dri, Fernando L.

AU - Shang, Shun Li

AU - Hector, Louis G.

AU - Saxe, Paul

AU - Liu, Zi Kui

AU - Moon, Robert J.

AU - Zavattieri, Pablo D.

PY - 2014/12/1

Y1 - 2014/12/1

N2 - Anisotropy 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, CijS (T) and CijT (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.

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