skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Quasi-Harmonic Lattice Dynamics of a Prototypical Metal–Organic Framework

Abstract

Quasi-harmonic lattice-dynamical calculations are performed to investigate the combined effect of temperature and pressure on the structural and mechanical properties of a prototypical metal–organic framework material: MOF-5. The softening upon compression of an A 2 g phonon mode at the Γ point in the high-symmetry F m 3 ¯ m structure is identified, which leads to a symmetry reduction and a group–subgroup phase transition to a low-symmetry F m 3 ¯ phase for compressions larger than 0.8%. The effect of the symmetry reduction on the equation-of-state of MOF-5 is investigated, which provides a static bulk modulus K reducing from 17 to 14 GPa and a corresponding change of K ' (pressure derivative of K) from positive to negative. The effect of pressure on the negative thermal expansion of the framework and on its mechanical response is analyzed. The evolution of the mechanical anisotropy of MOF-5 as a function of pressure is also determined, which allows identifying the occurrence of a shear-induced mechanical instability at 0.45 GPa.

Authors:
 [1]; ORCiD logo [2];  [2]; ORCiD logo [2]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Univ. of Torino (Italy)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1607147
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Theory and Simulations
Additional Journal Information:
Journal Volume: 2; Journal Issue: 11; Journal ID: ISSN 2513-0390
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Ryder, Matthew R., Maul, Jefferson, Civalleri, Bartolomeo, and Erba, Alessandro. Quasi-Harmonic Lattice Dynamics of a Prototypical Metal–Organic Framework. United States: N. p., 2019. Web. https://doi.org/10.1002/adts.201900093.
Ryder, Matthew R., Maul, Jefferson, Civalleri, Bartolomeo, & Erba, Alessandro. Quasi-Harmonic Lattice Dynamics of a Prototypical Metal–Organic Framework. United States. https://doi.org/10.1002/adts.201900093
Ryder, Matthew R., Maul, Jefferson, Civalleri, Bartolomeo, and Erba, Alessandro. Fri . "Quasi-Harmonic Lattice Dynamics of a Prototypical Metal–Organic Framework". United States. https://doi.org/10.1002/adts.201900093. https://www.osti.gov/servlets/purl/1607147.
@article{osti_1607147,
title = {Quasi-Harmonic Lattice Dynamics of a Prototypical Metal–Organic Framework},
author = {Ryder, Matthew R. and Maul, Jefferson and Civalleri, Bartolomeo and Erba, Alessandro},
abstractNote = {Quasi-harmonic lattice-dynamical calculations are performed to investigate the combined effect of temperature and pressure on the structural and mechanical properties of a prototypical metal–organic framework material: MOF-5. The softening upon compression of an A 2 g phonon mode at the Γ point in the high-symmetry F m 3 ¯ m structure is identified, which leads to a symmetry reduction and a group–subgroup phase transition to a low-symmetry F m 3 ¯ phase for compressions larger than 0.8%. The effect of the symmetry reduction on the equation-of-state of MOF-5 is investigated, which provides a static bulk modulus K reducing from 17 to 14 GPa and a corresponding change of K ' (pressure derivative of K) from positive to negative. The effect of pressure on the negative thermal expansion of the framework and on its mechanical response is analyzed. The evolution of the mechanical anisotropy of MOF-5 as a function of pressure is also determined, which allows identifying the occurrence of a shear-induced mechanical instability at 0.45 GPa.},
doi = {10.1002/adts.201900093},
journal = {Advanced Theory and Simulations},
number = 11,
volume = 2,
place = {United States},
year = {2019},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Explaining the mechanical mechanisms of zeolitic metal–organic frameworks: revealing auxeticity and anomalous elasticity
journal, January 2016

  • Ryder, Matthew. R.; Tan, Jin-Chong
  • Dalton Trans., Vol. 45, Issue 10
  • DOI: 10.1039/C5DT03514G

Density-Functional Perturbation Theory for Quasi-Harmonic Calculations
journal, January 2010

  • Baroni, S.; Giannozzi, P.; Isaev, E.
  • Reviews in Mineralogy and Geochemistry, Vol. 71, Issue 1
  • DOI: 10.2138/rmg.2010.71.3

The role of density functional theory methods in the prediction of nanostructured gas-adsorbent materials
journal, September 2015


Identifying the Role of Terahertz Vibrations in Metal-Organic Frameworks: From Gate-Opening Phenomenon to Shear-Driven Structural Destabilization
journal, November 2014


Pressure-volume-temperature relations in MgO: An ultrahigh pressure-temperature scale for planetary sciences applications
journal, January 2008

  • Wu, Zhongqing; Wentzcovitch, Renata M.; Umemoto, Koichiro
  • Journal of Geophysical Research, Vol. 113, Issue B6
  • DOI: 10.1029/2007JB005275

Elastic properties of six silicate garnet end members from accurate ab initio simulations
journal, October 2013

  • Erba, Alessandro; Mahmoud, Agnes; Orlando, Roberto
  • Physics and Chemistry of Minerals, Vol. 41, Issue 2
  • DOI: 10.1007/s00269-013-0630-4

Energy Ranking of Molecular Crystals Using Density Functional Theory Calculations and an Empirical van der Waals Correction
journal, August 2005

  • Neumann, Marcus A.; Perrin, Marc-Antoine
  • The Journal of Physical Chemistry B, Vol. 109, Issue 32
  • DOI: 10.1021/jp050121r

Pressure-driven mechanical anisotropy and destabilization in zeolitic imidazolate frameworks
journal, January 2019


Effect of gas pressure on negative thermal expansion in MOF-5
journal, January 2013

  • Lock, Nina; Christensen, Mogens; Kepert, Cameron J.
  • Chem. Commun., Vol. 49, Issue 8
  • DOI: 10.1039/C2CC37415C

Predicting finite-temperature properties of crystalline carbon dioxide from first principles with quantitative accuracy
journal, January 2016

  • Heit, Yonaton N.; Nanda, Kaushik D.; Beran, Gregory J. O.
  • Chemical Science, Vol. 7, Issue 1
  • DOI: 10.1039/C5SC03014E

Nuclear-relaxed elastic and piezoelectric constants of materials: Computational aspects of two quantum-mechanical approaches
journal, December 2016

  • Erba, Alessandro; Caglioti, Dominique; Zicovich-Wilson, Claudio Marcelo
  • Journal of Computational Chemistry, Vol. 38, Issue 5
  • DOI: 10.1002/jcc.24687

Acoustic phonons and negative thermal expansion in MOF-5
journal, January 2014

  • Rimmer, Leila H. N.; Dove, Martin T.; Goodwin, Andrew L.
  • Phys. Chem. Chem. Phys., Vol. 16, Issue 39
  • DOI: 10.1039/C4CP01701C

Enhancement of DFT-calculations at petascale: Nuclear Magnetic Resonance, Hybrid Density Functional Theory and Car–Parrinello calculations
journal, August 2013

  • Varini, Nicola; Ceresoli, Davide; Martin-Samos, Layla
  • Computer Physics Communications, Vol. 184, Issue 8
  • DOI: 10.1016/j.cpc.2013.03.003

Thermodynamic properties of CaCO3 calcite and aragonite: A quasi-harmonic calculation
journal, February 1993

  • Catti, M.; Pavese, A.; Price, G. D.
  • Physics and Chemistry of Minerals, Vol. 19, Issue 7
  • DOI: 10.1007/BF00203187

Scrutinizing negative thermal expansion in MOF-5 by scattering techniques and ab initio calculations
journal, January 2013

  • Lock, Nina; Christensen, Mogens; Wu, Yue
  • Dalton Trans., Vol. 42, Issue 6
  • DOI: 10.1039/C2DT31491F

Intermolecular anharmonicity in molecular crystals: interplay between experimental low-frequency dynamics and quantum quasi-harmonic simulations of solid purine
journal, January 2017

  • Ruggiero, Michael T.; Zeitler, J. Axel; Erba, Alessandro
  • Chemical Communications, Vol. 53, Issue 26
  • DOI: 10.1039/C7CC00509A

Assessing thermochemical properties of materials through ab initio quantum-mechanical methods: the case of α-Al 2 O 3
journal, January 2015

  • Erba, Alessandro; Maul, Jefferson; Demichelis, Raffaella
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 17
  • DOI: 10.1039/C5CP01537E

DFT-D3 Study of Some Molecular Crystals
journal, March 2014

  • Moellmann, Jonas; Grimme, Stefan
  • The Journal of Physical Chemistry C, Vol. 118, Issue 14
  • DOI: 10.1021/jp501237c

Energetic materials: variable-temperature crystal structures of γ- and ∊-HNIW polymorphs
journal, September 2004

  • Bolotina, Nadezhda B.; Hardie, Michaele J.; Speer Jr, Richard L.
  • Journal of Applied Crystallography, Vol. 37, Issue 5
  • DOI: 10.1107/S0021889804017832

On combining temperature and pressure effects on structural properties of crystals with standard ab initio techniques
journal, September 2014

  • Erba, A.
  • The Journal of Chemical Physics, Vol. 141, Issue 12
  • DOI: 10.1063/1.4896228

Thermodynamics of the Flexible Metal–Organic Framework Material MIL-53(Cr) From First-Principles
journal, February 2017


Elucidating Negative Thermal Expansion in MOF-5
journal, September 2010

  • Lock, Nina; Wu, Yue; Christensen, Mogens
  • The Journal of Physical Chemistry C, Vol. 114, Issue 39
  • DOI: 10.1021/jp103212z

Understanding and Controlling the Dielectric Response of Metal-Organic Frameworks
journal, March 2018

  • Ryder, Matthew R.; Donà, Lorenzo; Vitillo, Jenny G.
  • ChemPlusChem, Vol. 83, Issue 4
  • DOI: 10.1002/cplu.201700558

Thermal Expansion of Carbamazepine: Systematic Crystallographic Measurements Challenge Quantum Chemical Calculations
journal, August 2017

  • Brandenburg, Jan Gerit; Potticary, Jason; Sparkes, Hazel A.
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 17
  • DOI: 10.1021/acs.jpclett.7b01944

Exceptional Negative Thermal Expansion in Isoreticular Metal–Organic Frameworks
journal, June 2007

  • Dubbeldam, David; Walton, Krista S.; Ellis, Donald E.
  • Angewandte Chemie, Vol. 119, Issue 24
  • DOI: 10.1002/ange.200700218

Magnetoelastic coupling in the cobalt adipate metal–organic framework from quasi-harmonic lattice dynamics
journal, January 2015

  • Svane, Katrine L.; Saines, Paul J.; Walsh, Aron
  • Journal of Materials Chemistry C, Vol. 3, Issue 42
  • DOI: 10.1039/C5TC02633D

First-principles modeling of molecular crystals: structures and stabilities, temperature and pressure: First-principles modeling of molecular crystals
journal, December 2016

  • Hoja, Johannes; Reilly, Anthony M.; Tkatchenko, Alexandre
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 7, Issue 1
  • DOI: 10.1002/wcms.1294

Thermal decomposition of energetic materials. 61. Perfidy in the amino-2,4,6-trinitrobenzene series of explosives
journal, August 1993

  • Brill, T. B.; James, K. J.
  • The Journal of Physical Chemistry, Vol. 97, Issue 34
  • DOI: 10.1021/j100136a017

The Effect of High Pressure on MOF-5: Guest-Induced Modification of Pore Size and Content at High Pressure
journal, October 2011

  • Graham, Alexander J.; Allan, David R.; Muszkiewicz, Anna
  • Angewandte Chemie International Edition, Vol. 50, Issue 47
  • DOI: 10.1002/anie.201104285

Fully optimized contracted Gaussian basis sets for atoms Li to Kr
journal, August 1992

  • Schäfer, Ansgar; Horn, Hans; Ahlrichs, Reinhart
  • The Journal of Chemical Physics, Vol. 97, Issue 4
  • DOI: 10.1063/1.463096

Calculation of Dynamical Surface Properties of Noble-Gas Crystals. I. The Quasiharmonic Approximation
journal, March 1969


How important is thermal expansion for predicting molecular crystal structures and thermochemistry at finite temperatures?
journal, July 2016

  • Heit, Yonaton N.; Beran, Gregory J. O.
  • Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 72, Issue 4
  • DOI: 10.1107/S2052520616005382

Tracking thermal-induced amorphization of a zeolitic imidazolate framework via synchrotron in situ far-infrared spectroscopy
journal, January 2017

  • Ryder, Matthew R.; Bennett, Thomas D.; Kelley, Chris S.
  • Chemical Communications, Vol. 53, Issue 52
  • DOI: 10.1039/C7CC01985H

A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Large-Scale Condensed Matter DFT Simulations: Performance and Capabilities of the CRYSTAL Code
journal, September 2017

  • Erba, A.; Baima, J.; Bush, I.
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 10
  • DOI: 10.1021/acs.jctc.7b00687

Microscopic Mechanism of Chiral Induction in a Metal–Organic Framework
journal, May 2016

  • Evans, Jack D.; Coudert, François-Xavier
  • Journal of the American Chemical Society, Vol. 138, Issue 19
  • DOI: 10.1021/jacs.6b02781

Probing the dynamics of instability in zeolitic materials
journal, August 2004


Investigating the Pressure-Induced Amorphization of Zeolitic Imidazolate Framework ZIF-8: Mechanical Instability Due to Shear Mode Softening
journal, May 2013

  • Ortiz, Aurélie U.; Boutin, Anne; Fuchs, Alain H.
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 11
  • DOI: 10.1021/jz400880p

Thermal properties of molecular crystals through dispersion-corrected quasi-harmonic ab initio calculations: the case of urea
journal, January 2016

  • Erba, Alessandro; Maul, Jefferson; Civalleri, Bartolomeo
  • Chemical Communications, Vol. 52, Issue 9
  • DOI: 10.1039/C5CC08982D

Quantum-mechanical condensed matter simulations with CRYSTAL
journal, March 2018

  • Dovesi, Roberto; Erba, Alessandro; Orlando, Roberto
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 8, Issue 4
  • DOI: 10.1002/wcms.1360

Exceptional Negative Thermal Expansion in Isoreticular Metal–Organic Frameworks
journal, June 2007

  • Dubbeldam, David; Walton, Krista S.; Ellis, Donald E.
  • Angewandte Chemie International Edition, Vol. 46, Issue 24
  • DOI: 10.1002/anie.200700218

Anisotropic displacement parameters for molecular crystals from periodic Hartree–Fock and density functional theory calculations
journal, April 2013

  • Madsen, Anders Østergaard; Civalleri, Bartolomeo; Ferrabone, Matteo
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 69, Issue 3
  • DOI: 10.1107/S0108767313005011

Anharmonic Vibrational States of Solids from DFT Calculations. Part II: Implementation of the VSCF and VCI Methods
journal, April 2019

  • Erba, Alessandro; Maul, Jefferson; Ferrabone, Matteo
  • Journal of Chemical Theory and Computation, Vol. 15, Issue 6
  • DOI: 10.1021/acs.jctc.9b00294

Identifying Vibrations That Destabilize Crystals and Characterize the Glassy State
journal, May 2005


Ab initio calculation of structural and lattice-dynamical properties of silicon carbide
journal, December 1994


Large negative thermal expansion provided by metal-organic framework MOF-5: A first-principles study
journal, June 2016


Anharmonic Vibrational States of Solids from DFT Calculations. Part I: Description of the Potential Energy Surface
journal, April 2019

  • Erba, Alessandro; Maul, Jefferson; Ferrabone, Matteo
  • Journal of Chemical Theory and Computation, Vol. 15, Issue 6
  • DOI: 10.1021/acs.jctc.9b00293

Influence of the exchange-correlation functional on the quasi-harmonic lattice dynamics of II-VI semiconductors
journal, August 2015

  • Skelton, Jonathan M.; Tiana, Davide; Parker, Stephen C.
  • The Journal of Chemical Physics, Vol. 143, Issue 6
  • DOI: 10.1063/1.4928058

Toward Computational Materials Design: The Impact of Density Functional Theory on Materials Research
journal, September 2006

  • Hafner, Jürgen; Wolverton, Christopher; Ceder, Gerbrand
  • MRS Bulletin, Vol. 31, Issue 9
  • DOI: 10.1557/mrs2006.174

Metal−Organic Frameworks Provide Large Negative Thermal Expansion Behavior
journal, October 2007

  • Han, Sang Soo; Goddard, William A.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 42
  • DOI: 10.1021/jp075389s

Detecting Molecular Rotational Dynamics Complementing the Low-Frequency Terahertz Vibrations in a Zirconium-Based Metal-Organic Framework
journal, June 2017


On how differently the quasi-harmonic approximation works for two isostructural crystals: Thermal properties of periclase and lime
journal, January 2015

  • Erba, A.; Shahrokhi, M.; Moradian, R.
  • The Journal of Chemical Physics, Vol. 142, Issue 4
  • DOI: 10.1063/1.4906422

Accurate and Efficient Method for Many-Body van der Waals Interactions
journal, June 2012


Calculation of Thermal Expansion, Compressiblity, an Melting in Alkali Halides: NaCl and KCl
journal, February 1979


Structural and elastic anisotropy of crystals at high pressures and temperatures from quantum mechanical methods: The case of Mg 2 SiO 4 forsterite
journal, May 2015

  • Erba, A.; Maul, J.; De La Pierre, M.
  • The Journal of Chemical Physics, Vol. 142, Issue 20
  • DOI: 10.1063/1.4921781

Static and lattice vibrational energy differences between polymorphs
journal, January 2015


Discovering connections between terahertz vibrations and elasticity underpinning the collective dynamics of the HKUST-1 metal–organic framework
journal, January 2016

  • Ryder, Matthew R.; Civalleri, Bartolomeo; Cinque, Gianfelice
  • CrystEngComm, Vol. 18, Issue 23
  • DOI: 10.1039/C5CE02347E

Isoreticular zirconium-based metal–organic frameworks: discovering mechanical trends and elastic anomalies controlling chemical structure stability
journal, January 2016

  • Ryder, Matthew R.; Civalleri, Bartolomeo; Tan, Jin-Chong
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 13
  • DOI: 10.1039/C6CP00864J

Introducing k-point parallelism into VASP
journal, August 2012

  • Maniopoulou, Asimina; Davidson, Erlend R. M.; Grau-Crespo, Ricardo
  • Computer Physics Communications, Vol. 183, Issue 8
  • DOI: 10.1016/j.cpc.2012.03.009

Thermo-Elasticity of Materials from Quasi-Harmonic Calculations
journal, December 2018

  • Destefanis, Maurizio; Ravoux, Corentin; Cossard, Alessandro
  • Minerals, Vol. 9, Issue 1
  • DOI: 10.3390/min9010016

Thermodynamic Properties of Molecular Crystals Calculated within the Quasi-Harmonic Approximation
journal, March 2016

  • Červinka, Ctirad; Fulem, Michal; Stoffel, Ralf Peter
  • The Journal of Physical Chemistry A, Vol. 120, Issue 12
  • DOI: 10.1021/acs.jpca.6b00401

In silico design and screening of hypothetical MOF-74 analogs and their experimental synthesis
journal, January 2016

  • Witman, Matthew; Ling, Sanliang; Anderson, Samantha
  • Chemical Science, Vol. 7, Issue 9
  • DOI: 10.1039/C6SC01477A

Thermal properties of the orthorhombic CaSnO3 perovskite under pressure from ab initio quasi-harmonic calculations
journal, January 2016

  • Maul, J.; Santos, I. M. G.; Sambrano, J. R.
  • Theoretical Chemistry Accounts, Vol. 135, Issue 2
  • DOI: 10.1007/s00214-015-1765-9

C RYSTAL14 : A program for the ab initio investigation of crystalline solids
journal, March 2014

  • Dovesi, Roberto; Orlando, Roberto; Erba, Alessandro
  • International Journal of Quantum Chemistry, Vol. 114, Issue 19
  • DOI: 10.1002/qua.24658

Understanding the role of vibrations, exact exchange, and many-body van der Waals interactions in the cohesive properties of molecular crystals
journal, July 2013

  • Reilly, Anthony M.; Tkatchenko, Alexandre
  • The Journal of Chemical Physics, Vol. 139, Issue 2
  • DOI: 10.1063/1.4812819

The rheology of collapsing zeolites amorphized by temperature and pressure
journal, August 2003

  • Greaves, G. N.; Meneau, F.; Sapelkin, A.
  • Nature Materials, Vol. 2, Issue 9
  • DOI: 10.1038/nmat963

Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr
journal, April 1994

  • Schäfer, Ansgar; Huber, Christian; Ahlrichs, Reinhart
  • The Journal of Chemical Physics, Vol. 100, Issue 8
  • DOI: 10.1063/1.467146

Vibrational and quasiharmonic thermal properties of CaO under pressure
journal, December 2003


High pressure elastic properties of minerals from ab initio simulations: The case of pyrope, grossular and andradite silicate garnets
journal, March 2014

  • Erba, A.; Mahmoud, A.; Belmonte, D.
  • The Journal of Chemical Physics, Vol. 140, Issue 12
  • DOI: 10.1063/1.4869144

B3LYP augmented with an empirical dispersion term (B3LYP-D*) as applied to molecular crystals
journal, January 2008

  • Civalleri, Bartolomeo; Zicovich-Wilson, Claudio M.; Valenzano, Loredana
  • CrystEngComm, Vol. 10, Issue 4
  • DOI: 10.1039/B715018K

Computational characterization and prediction of metal–organic framework properties
journal, January 2016


cp2k: atomistic simulations of condensed matter systems
journal, June 2013

  • Hutter, Jürg; Iannuzzi, Marcella; Schiffmann, Florian
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 1
  • DOI: 10.1002/wcms.1159

Exchange-Hole Dipole Dispersion Model for Accurate Energy Ranking in Molecular Crystal Structure Prediction
journal, January 2017

  • Whittleton, Sarah R.; Otero-de-la-Roza, A.; Johnson, Erin R.
  • Journal of Chemical Theory and Computation, Vol. 13, Issue 2
  • DOI: 10.1021/acs.jctc.6b00679

Probing the Mechanochemistry of Metal–Organic Frameworks with Low-Frequency Vibrational Spectroscopy
journal, November 2018

  • Zhang, Wei; Maul, Jefferson; Vulpe, Diana
  • The Journal of Physical Chemistry C, Vol. 122, Issue 48
  • DOI: 10.1021/acs.jpcc.8b08334