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

Title: Thermal expansion in dispersion-bound molecular crystals

Abstract

In this paper, we explore how anharmonicity, nuclear quantum effects (NQE), many-body dispersion interactions, and Pauli repulsion influence thermal properties of dispersion-bound molecular crystals. Accounting for anharmonicity with ab initio molecular dynamics yields cell parameters accurate to within 2% of experiment for a set of pyridinelike molecular crystals at finite temperatures and pressures. From the experimental thermal expansion curve, we find that pyridine-I has a Debye temperature just above its melting point, indicating sizable NQE across the entire crystalline range of stability. We find that NQE lead to a substantial volume increase in pyridine-I (≈ 40% more than classical thermal expansion at 153 K) and attribute this to intermolecular Pauli repulsion promoted by intramolecular quantum fluctuations. Finally, when predicting delicate properties such as the thermal expansivity, we show that many-body dispersion interactions and more sophisticated density functional approximations improve the accuracy of the theoretical model.

Authors:
 [1];  [2];  [1];  [3]
  1. Princeton Univ., Princeton, NJ (United States). Dept. of Chemistry
  2. Cornell Univ., Ithaca, NY (United States). Dept. of Chemistry and Chemical Biology
  3. Princeton Univ., Princeton, NJ (United States). Dept. of Chemistry. Dept. of Physics
Publication Date:
Research Org.:
Princeton Univ., NJ (United States); Cornell Univ., Ithaca, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
OSTI Identifier:
1437639
Alternate Identifier(s):
OSTI ID: 1437687
Grant/Contract Number:  
SC0008626; SC0005180; AC02-05CH11231; AC02-06CH11357; DMR-1719875
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 2; Journal Issue: 5; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 74 ATOMIC AND MOLECULAR PHYSICS; crystal structure; density functional theory; structural properties; thermal expansion; thermal properties; Van der Waals interaction

Citation Formats

Ko, Hsin -Yu, DiStasio, Robert A., Santra, Biswajit, and Car, Roberto. Thermal expansion in dispersion-bound molecular crystals. United States: N. p., 2018. Web. doi:10.1103/PhysRevMaterials.2.055603.
Ko, Hsin -Yu, DiStasio, Robert A., Santra, Biswajit, & Car, Roberto. Thermal expansion in dispersion-bound molecular crystals. United States. doi:10.1103/PhysRevMaterials.2.055603.
Ko, Hsin -Yu, DiStasio, Robert A., Santra, Biswajit, and Car, Roberto. Fri . "Thermal expansion in dispersion-bound molecular crystals". United States. doi:10.1103/PhysRevMaterials.2.055603. https://www.osti.gov/servlets/purl/1437639.
@article{osti_1437639,
title = {Thermal expansion in dispersion-bound molecular crystals},
author = {Ko, Hsin -Yu and DiStasio, Robert A. and Santra, Biswajit and Car, Roberto},
abstractNote = {In this paper, we explore how anharmonicity, nuclear quantum effects (NQE), many-body dispersion interactions, and Pauli repulsion influence thermal properties of dispersion-bound molecular crystals. Accounting for anharmonicity with ab initio molecular dynamics yields cell parameters accurate to within 2% of experiment for a set of pyridinelike molecular crystals at finite temperatures and pressures. From the experimental thermal expansion curve, we find that pyridine-I has a Debye temperature just above its melting point, indicating sizable NQE across the entire crystalline range of stability. We find that NQE lead to a substantial volume increase in pyridine-I (≈ 40% more than classical thermal expansion at 153 K) and attribute this to intermolecular Pauli repulsion promoted by intramolecular quantum fluctuations. Finally, when predicting delicate properties such as the thermal expansivity, we show that many-body dispersion interactions and more sophisticated density functional approximations improve the accuracy of the theoretical model.},
doi = {10.1103/PhysRevMaterials.2.055603},
journal = {Physical Review Materials},
number = 5,
volume = 2,
place = {United States},
year = {2018},
month = {5}
}

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

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Figures / Tables:

FIG. 1 FIG. 1: Predicted cell volumes (Vpred) from VC optimizations and AIMD simulations using PBE + vdW$TS\atop{SC}$ for the PLMC set. Errors are defined with respect to experiment (Vexpt) at the indicated thermodynamic conditions as Verr = (Vpred − Vexpt)/Vexpt. Inset: Overlay of predicted (blue) and experimental (red) [40] pyridine-I structures.

Save / Share:

Works referenced in this record:

Order- N implementation of exact exchange in extended insulating systems
journal, February 2009


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Physical adsorption at the nanoscale: Towards controllable scaling of the substrate-adsorbate van der Waals interaction
journal, June 2017

  • Ambrosetti, Alberto; Silvestrelli, Pier Luigi; Tkatchenko, Alexandre
  • Physical Review B, Vol. 95, Issue 23
  • DOI: 10.1103/PhysRevB.95.235417

Exchange-hole dipole moment and the dispersion interaction revisited
journal, October 2007

  • Becke, Axel D.; Johnson, Erin R.
  • The Journal of Chemical Physics, Vol. 127, Issue 15
  • DOI: 10.1063/1.2795701

Interaction of the van der Waals Type Between Three Atoms
journal, June 1943

  • Axilrod, B. M.; Teller, E.
  • The Journal of Chemical Physics, Vol. 11, Issue 6
  • DOI: 10.1063/1.1723844

Design and Synthesis of Energetic Materials
journal, August 2001


Ab initio Calculation of van der Waals Bonded Molecular Crystals
journal, May 2009


QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

van der Waals Volumes and Radii
journal, March 1964

  • Bondi, A.
  • The Journal of Physical Chemistry, Vol. 68, Issue 3, p. 441-451
  • DOI: 10.1021/j100785a001

Exploiting the isomorphism between quantum theory and classical statistical mechanics of polyatomic fluids
journal, April 1981

  • Chandler, David; Wolynes, Peter G.
  • The Journal of Chemical Physics, Vol. 74, Issue 7
  • DOI: 10.1063/1.441588

Molecular dynamics simulations of a protein in the canonical ensemble
journal, December 1993

  • Tobias, Douglas J.; Martyna, Glenn J.; Klein, Michael L.
  • The Journal of Physical Chemistry, Vol. 97, Issue 49
  • DOI: 10.1021/j100151a052

First-Principles Models for van der Waals Interactions in Molecules and Materials: Concepts, Theory, and Applications
journal, March 2017


Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data
journal, February 2009


i-PI: A Python interface for ab initio path integral molecular dynamics simulations
journal, March 2014

  • Ceriotti, Michele; More, Joshua; Manolopoulos, David E.
  • Computer Physics Communications, Vol. 185, Issue 3
  • DOI: 10.1016/j.cpc.2013.10.027

Second Harmonic Generation from a Homologous Series of Molecular Crystals: Impact of Supramolecular Interactions
journal, June 2006

  • Prakash, M. Jaya; Radhakrishnan, T. P.
  • Chemistry of Materials, Vol. 18, Issue 13
  • DOI: 10.1021/cm052607q

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

A new mixing of Hartree–Fock and local density‐functional theories
journal, January 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 2
  • DOI: 10.1063/1.464304

Isotopic Polymorphism in Pyridine
journal, January 2009

  • Crawford, Stephen; Kirchner, Michael T.; Bläser, Dieter
  • Angewandte Chemie International Edition, Vol. 48, Issue 4
  • DOI: 10.1002/anie.200803589

Interatomic methods for the dispersion energy derived from the adiabatic connection fluctuation-dissipation theorem
journal, February 2013

  • Tkatchenko, Alexandre; Ambrosetti, Alberto; DiStasio, Robert A.
  • The Journal of Chemical Physics, Vol. 138, Issue 7
  • DOI: 10.1063/1.4789814

An Assessment of the vdW-TS Method for Extended Systems
journal, March 2012

  • Al-Saidi, W. A.; Voora, Vamsee K.; Jordan, Kenneth D.
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 4
  • DOI: 10.1021/ct200618b

Numerical Estimation of the Partition Function in Quantum Statistics
journal, November 1962

  • Fosdick, Lloyd D.
  • Journal of Mathematical Physics, Vol. 3, Issue 6
  • DOI: 10.1063/1.1703867

Report on the sixth blind test of organic crystal structure prediction methods
journal, August 2016

  • Reilly, Anthony M.; Cooper, Richard I.; Adjiman, Claire S.
  • Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 72, Issue 4
  • DOI: 10.1107/S2052520616007447

Unified Approach for Molecular Dynamics and Density-Functional Theory
journal, November 1985


Accelerating the convergence of path integral dynamics with a generalized Langevin equation
journal, February 2011

  • Ceriotti, Michele; Manolopoulos, David E.; Parrinello, Michele
  • The Journal of Chemical Physics, Vol. 134, Issue 8
  • DOI: 10.1063/1.3556661

Perturbed path integrals in imaginary time: Efficiently modeling nuclear quantum effects in molecules and materials
journal, March 2018

  • Poltavsky, Igor; DiStasio, Robert A.; Tkatchenko, Alexandre
  • The Journal of Chemical Physics, Vol. 148, Issue 10
  • DOI: 10.1063/1.5006596

Crystal Structure and Pair Potentials: A Molecular-Dynamics Study
journal, October 1980


LI. A new treatment of anharmonicity in lattice thermodynamics: I
journal, April 1955

  • Hooton, D. J.
  • The London, Edinburgh, and Dublin Philosophical Magazine and Journal of Science, Vol. 46, Issue 375
  • DOI: 10.1080/14786440408520575

van der Waals forces in density functional theory: a review of the vdW-DF method
journal, May 2015


Nuclear Quantum Effects in Solids Using a Colored-Noise Thermostat
journal, July 2009


Insights into Current Limitations of Density Functional Theory
journal, August 2008


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

Crystal structures of pyridine and pyridine trihydrate
journal, August 1981

  • Mootz, D.; Wussow, H. ‐G.
  • The Journal of Chemical Physics, Vol. 75, Issue 3
  • DOI: 10.1063/1.442204

Pyrrole and a Co-crystal of 1 H - and 2 H -1,2,3-Triazole
journal, December 1997

  • Goddard, R.; Heinemann, O.; Krüger, C.
  • Acta Crystallographica Section C Crystal Structure Communications, Vol. 53, Issue 12
  • DOI: 10.1107/S0108270197009682

Ab initio path integral molecular dynamics: Basic ideas
journal, March 1996

  • Marx, Dominik; Parrinello, Michele
  • The Journal of Chemical Physics, Vol. 104, Issue 11
  • DOI: 10.1063/1.471221

Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965


Thermal expansion coefficient of single-crystal silicon from 7 K to 293 K
journal, November 2015


Long-range correlation energy calculated from coupled atomic response functions
journal, May 2014

  • Ambrosetti, Alberto; Reilly, Anthony M.; DiStasio, Robert A.
  • The Journal of Chemical Physics, Vol. 140, Issue 18
  • DOI: 10.1063/1.4865104

First-principle-constant pressure molecular dynamics
journal, March 1995

  • Bernasconi, M.; Chiarotti, G. L.; Focher, P.
  • Journal of Physics and Chemistry of Solids, Vol. 56, Issue 3-4
  • DOI: 10.1016/0022-3697(94)00228-2

Hard Numbers for Large Molecules: Toward Exact Energetics for Supramolecular Systems
journal, February 2014

  • Ambrosetti, Alberto; Alfè, Dario; DiStasio, Robert A.
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 5
  • DOI: 10.1021/jz402663k

Collective many-body van der Waals interactions in molecular systems
journal, August 2012

  • DiStasio, R. A.; von Lilienfeld, O. A.; Tkatchenko, A.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 37
  • DOI: 10.1073/pnas.1208121109

First-Principles Theory of Anharmonicity and the Inverse Isotope Effect in Superconducting Palladium-Hydride Compounds
journal, October 2013


The individual and collective effects of exact exchange and dispersion interactions on the ab initio structure of liquid water
journal, August 2014

  • DiStasio, Robert A.; Santra, Biswajit; Li, Zhaofeng
  • The Journal of Chemical Physics, Vol. 141, Issue 8
  • DOI: 10.1063/1.4893377

Analytical nuclear gradients for the range-separated many-body dispersion model of noncovalent interactions
journal, January 2016

  • Blood-Forsythe, Martin A.; Markovich, Thomas; DiStasio, Robert A.
  • Chemical Science, Vol. 7, Issue 3
  • DOI: 10.1039/C5SC03234B

Higher-accuracy van der Waals density functional
journal, August 2010


Computational prediction of organic crystal structures and polymorphism
journal, July 2008


From crystal structure prediction to polymorph prediction: interpreting the crystal energy landscape
journal, January 2008

  • Price, Sarah L.
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 15
  • DOI: 10.1039/b719351c

Dispersion-Corrected Mean-Field Electronic Structure Methods
journal, April 2016


Efficient and general algorithms for path integral Car–Parrinello molecular dynamics
journal, April 1996

  • Tuckerman, Mark E.; Marx, Dominik; Klein, Michael L.
  • The Journal of Chemical Physics, Vol. 104, Issue 14
  • DOI: 10.1063/1.471771

Perspective: Advances and challenges in treating van der Waals dispersion forces in density functional theory
journal, September 2012

  • Klimeš, Jiří; Michaelides, Angelos
  • The Journal of Chemical Physics, Vol. 137, Issue 12
  • DOI: 10.1063/1.4754130

Inhomogeneous Electron Gas
journal, November 1964


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


Electronic Properties of Molecules and Surfaces with a Self-Consistent Interatomic van der Waals Density Functional
journal, April 2015


Density, freezing and molecular aggregation in pyridazine, pyridine and benzene
journal, January 2010

  • Podsiadło, Marcin; Jakóbek, Katarzyna; Katrusiak, Andrzej
  • CrystEngComm, Vol. 12, Issue 9
  • DOI: 10.1039/c001153c

Crystal engineering of the composition of pharmaceutical phases. Do pharmaceutical co-crystals represent a new path to improved medicines?
journal, January 2004

  • Almarsson, �rn; Zaworotko, Michael J.
  • Chemical Communications, Issue 17
  • DOI: 10.1039/b402150a

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

Wavelike charge density fluctuations and van der Waals interactions at the nanoscale
journal, March 2016

  • Ambrosetti, Alberto; Ferri, Nicola; DiStasio, Robert A.
  • Science, Vol. 351, Issue 6278
  • DOI: 10.1126/science.aae0509

Many-body van der Waals interactions in molecules and condensed matter
journal, May 2014

  • DiStasio, Robert A.; Gobre, Vivekanand V.; Tkatchenko, Alexandre
  • Journal of Physics: Condensed Matter, Vol. 26, Issue 21
  • DOI: 10.1088/0953-8984/26/21/213202

Negative Linear Compressibility and Massive Anisotropic Thermal Expansion in Methanol Monohydrate
journal, February 2011


Many-Body Dispersion Interactions in Molecular Crystal Polymorphism
journal, May 2013

  • Marom, Noa; DiStasio, Robert A.; Atalla, Viktor
  • Angewandte Chemie International Edition, Vol. 52, Issue 26
  • DOI: 10.1002/anie.201301938

Rationale for mixing exact exchange with density functional approximations
journal, December 1996

  • Perdew, John P.; Ernzerhof, Matthias; Burke, Kieron
  • The Journal of Chemical Physics, Vol. 105, Issue 22, p. 9982-9985
  • DOI: 10.1063/1.472933

Nonlocal van der Waals Density Functional Made Simple
journal, August 2009


Advanced capabilities for materials modelling with Quantum ESPRESSO
journal, October 2017

  • Giannozzi, P.; Andreussi, O.; Brumme, T.
  • Journal of Physics: Condensed Matter, Vol. 29, Issue 46
  • DOI: 10.1088/1361-648X/aa8f79

    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.