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

Title: Assessment of two hybrid van der Waals density functionals for covalent and non-covalent binding of molecules

Abstract

Two hybrid van der Waals density functionals (vdW-DFs) are developed using 25% Fock exchange with (i) the consistent-exchange vdW-DF-cx functional [K. Berland and P. Hyldgaard, Phys. Rev. B 89, 035412 (2014)] and (ii) with the vdW-DF2 functional [K. Lee et al., Phys. Rev. B 82, 081101 (2010)]. The ability to describe covalent and non-covalent binding properties of molecules is assessed. For properties related to covalent binding, atomization energies (G2-1 set), molecular reaction energies (G2RC set), and ionization energies (G21IP set) are benchmarked against experimental reference values. We find that hybrid-vdW-DF-cx yields results that are rather similar to those of the standard non-empirical hybrid PBE0 [C. Adamo and V. Barone, J. Chem. Phys. 110, 6158 (1999)], with mean average deviations (MADs) of 4.9 and 5.0 kcal/mol for the G2-1 set, respectively. In this comparison, experimental reference values are used, back corrected by wavefunction-based quantum-chemistry calculations of zero-point energies. Hybrid vdW-DF2 follows somewhat different trends, showing on average significantly larger deviations from the reference energies, with a MAD of 14.5 kcal/mol for the G2-1 set. Non-covalent binding properties of molecules are assessed using the S22 benchmark set of non-covalently bonded dimers and the X40 set of dimers of small halogenated molecules, usingmore » wavefunction-based quantum chemistry results as references. For the S22 set, hybrid-vdW-DF-cx performs better than standard vdW-DF-cx for the mostly hydrogen-bonded systems, with MAD dropping from 0.6 to 0.3 kcal/mol, but worse for purely dispersion-bonded systems, with MAD increasing from 0.2 to 0.6 kcal/mol. Hybrid-vdW-DF2 offers a slight improvement over standard vdW-DF2. Similar trends are found for the X40 set, with hybrid-vdW-DF-cx performing particularly well for binding energies involving the strongly polar hydrogen halides, but poorly for systems with tiny binding energies. Our study of the X40 set reveals the potential of mixing Fock exchange with vdW-DF, but also highlights shortcomings of the hybrids constructed here. In conclusion, the solid performance of hybrid-vdW-DF-cx for covalent-bonded systems, as well as the strengths and issues uncovered for non-covalently bonded systems, makes this study a good starting point for developing even more accurate hybrid vdW-DFs.« less

Authors:
 [1]; ORCiD logo [2];  [3];  [3];  [4]; ORCiD logo [2]
  1. Univ. of Oslo, Oslo (Norway). Centre for Materials Science and Nanotechnology (SMN), Dept. of Physics
  2. Chalmers Univ. of Technology, Gothenburg (Sweden). Microtechnology and Nanoscience–MC2
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Univ. of California, Berkeley, CA (United States). Dept. of Physics
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Univ. of California, Berkeley, CA (United States). Dept. of Physics; Kavli Energy NanoScience Inst. at Berkeley, Berkeley, CA (United States)
Publication Date:
Research Org.:
Univ. of California, Berkeley, CA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Gas Separations Relevant to Clean Energy Technologies (CGS)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Swedish Research Council (SRC); Research Council of Norway; Swedish National Infrastructure for Computing (SNIC)
OSTI Identifier:
1388990
Alternate Identifier(s):
OSTI ID: 1364666
Grant/Contract Number:  
SC0001015; AC02-05CH11231; 2016-10-12
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 146; Journal Issue: 23; Related Information: CGS partners with University of California, Berkeley; University of California, Davis; Lawrence Berkeley National Laboratory; University of Minnesota; National Energy Technology Laboratory; Texas A&M University; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; membrane; carbon capture; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)

Citation Formats

Berland, Kristian, Jiao, Yang, Lee, Jung-Hoon, Rangel, Tonatiuh, Neaton, Jeffrey B., and Hyldgaard, Per. Assessment of two hybrid van der Waals density functionals for covalent and non-covalent binding of molecules. United States: N. p., 2017. Web. doi:10.1063/1.4986522.
Berland, Kristian, Jiao, Yang, Lee, Jung-Hoon, Rangel, Tonatiuh, Neaton, Jeffrey B., & Hyldgaard, Per. Assessment of two hybrid van der Waals density functionals for covalent and non-covalent binding of molecules. United States. doi:10.1063/1.4986522.
Berland, Kristian, Jiao, Yang, Lee, Jung-Hoon, Rangel, Tonatiuh, Neaton, Jeffrey B., and Hyldgaard, Per. Wed . "Assessment of two hybrid van der Waals density functionals for covalent and non-covalent binding of molecules". United States. doi:10.1063/1.4986522. https://www.osti.gov/servlets/purl/1388990.
@article{osti_1388990,
title = {Assessment of two hybrid van der Waals density functionals for covalent and non-covalent binding of molecules},
author = {Berland, Kristian and Jiao, Yang and Lee, Jung-Hoon and Rangel, Tonatiuh and Neaton, Jeffrey B. and Hyldgaard, Per},
abstractNote = {Two hybrid van der Waals density functionals (vdW-DFs) are developed using 25% Fock exchange with (i) the consistent-exchange vdW-DF-cx functional [K. Berland and P. Hyldgaard, Phys. Rev. B 89, 035412 (2014)] and (ii) with the vdW-DF2 functional [K. Lee et al., Phys. Rev. B 82, 081101 (2010)]. The ability to describe covalent and non-covalent binding properties of molecules is assessed. For properties related to covalent binding, atomization energies (G2-1 set), molecular reaction energies (G2RC set), and ionization energies (G21IP set) are benchmarked against experimental reference values. We find that hybrid-vdW-DF-cx yields results that are rather similar to those of the standard non-empirical hybrid PBE0 [C. Adamo and V. Barone, J. Chem. Phys. 110, 6158 (1999)], with mean average deviations (MADs) of 4.9 and 5.0 kcal/mol for the G2-1 set, respectively. In this comparison, experimental reference values are used, back corrected by wavefunction-based quantum-chemistry calculations of zero-point energies. Hybrid vdW-DF2 follows somewhat different trends, showing on average significantly larger deviations from the reference energies, with a MAD of 14.5 kcal/mol for the G2-1 set. Non-covalent binding properties of molecules are assessed using the S22 benchmark set of non-covalently bonded dimers and the X40 set of dimers of small halogenated molecules, using wavefunction-based quantum chemistry results as references. For the S22 set, hybrid-vdW-DF-cx performs better than standard vdW-DF-cx for the mostly hydrogen-bonded systems, with MAD dropping from 0.6 to 0.3 kcal/mol, but worse for purely dispersion-bonded systems, with MAD increasing from 0.2 to 0.6 kcal/mol. Hybrid-vdW-DF2 offers a slight improvement over standard vdW-DF2. Similar trends are found for the X40 set, with hybrid-vdW-DF-cx performing particularly well for binding energies involving the strongly polar hydrogen halides, but poorly for systems with tiny binding energies. Our study of the X40 set reveals the potential of mixing Fock exchange with vdW-DF, but also highlights shortcomings of the hybrids constructed here. In conclusion, the solid performance of hybrid-vdW-DF-cx for covalent-bonded systems, as well as the strengths and issues uncovered for non-covalently bonded systems, makes this study a good starting point for developing even more accurate hybrid vdW-DFs.},
doi = {10.1063/1.4986522},
journal = {Journal of Chemical Physics},
number = 23,
volume = 146,
place = {United States},
year = {2017},
month = {6}
}

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

Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Application of van der Waals Density Functional to an Extended System: Adsorption of Benzene and Naphthalene on Graphite
journal, April 2006

  • Chakarova-Käck, Svetla D.; Schröder, Elsebeth; Lundqvist, Bengt I.
  • Physical Review Letters, Vol. 96, Issue 14
  • DOI: 10.1103/physrevlett.96.146107

Nonlocal van der Waals density functional: The simpler the better
journal, December 2010

  • Vydrov, Oleg A.; Van Voorhis, Troy
  • The Journal of Chemical Physics, Vol. 133, Issue 24
  • DOI: 10.1063/1.3521275

Hybrid functionals based on a screened Coulomb potential
journal, May 2003

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 118, Issue 18
  • DOI: 10.1063/1.1564060

Spin Signature of Nonlocal Correlation Binding in Metal-Organic Frameworks
journal, September 2015


libvdwxc: a library for exchange–correlation functionals in the vdW-DF family
journal, June 2017

  • Larsen, Ask Hjorth; Kuisma, Mikael; Löfgren, Joakim
  • Modelling and Simulation in Materials Science and Engineering, Vol. 25, Issue 6
  • DOI: 10.1088/1361-651x/aa7320

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

Exact electron-gas response functions at high density
journal, July 1987


A density functional for sparse matter
journal, January 2009

  • Langreth, D. C.; Lundqvist, B. I.; Chakarova-Käck, S. D.
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 8
  • DOI: 10.1088/0953-8984/21/8/084203

Correlation Energy of a Free Electron Gas
journal, July 1958


The role of polymorphism in organic thin films: oligoacenes investigated from first principles
journal, December 2009


Efficient pseudopotentials for plane-wave calculations
journal, January 1991


A thorough benchmark of density functional methods for general main group thermochemistry, kinetics, and noncovalent interactions
journal, January 2011

  • Goerigk, Lars; Grimme, Stefan
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 14
  • DOI: 10.1039/c0cp02984j

Testing several recent van der Waals density functionals for layered structures
journal, August 2014

  • Björkman, Torbjörn
  • The Journal of Chemical Physics, Vol. 141, Issue 7
  • DOI: 10.1063/1.4893329

Benchmark Calculations of Noncovalent Interactions of Halogenated Molecules
journal, September 2012

  • Řezáč, Jan; Riley, Kevin E.; Hobza, Pavel
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 11
  • DOI: 10.1021/ct300647k

Erratum: “Hybrid functionals based on a screened Coulomb potential” [J. Chem. Phys. 118, 8207 (2003)]
journal, June 2006

  • Heyd, Jochen; Scuseria, Gustavo E.; Ernzerhof, Matthias
  • The Journal of Chemical Physics, Vol. 124, Issue 21
  • DOI: 10.1063/1.2204597

Benzene adsorbed on metals: Concerted effect of covalency and van der Waals bonding
journal, December 2012


Efficient Implementation of a van der Waals Density Functional: Application to Double-Wall Carbon Nanotubes
journal, August 2009


Desorption of n-alkanes from graphene: a van der Waals density functional study
journal, October 2012


Structural and excited-state properties of oligoacene crystals from first principles
journal, March 2016


Exchange-correlation energy of a metallic surface: Wave-vector analysis
journal, March 1977


Interpretation of van der Waals density functionals
journal, August 2014


van der Waals density functional made accurate
journal, March 2014


Investigation of Exchange Energy Density Functional Accuracy for Interacting Molecules
journal, August 2009

  • Murray, Éamonn D.; Lee, Kyuho; Langreth, David C.
  • Journal of Chemical Theory and Computation, Vol. 5, Issue 10
  • DOI: 10.1021/ct900365q

A van der Waals density functional study of adenine on graphene: single-molecular adsorption and overlayer binding
journal, March 2011

  • Berland, Kristian; Chakarova-Käck, Svetla D.; Cooper, Valentino R.
  • Journal of Physics: Condensed Matter, Vol. 23, Issue 13
  • DOI: 10.1088/0953-8984/23/13/135001

Erratum: Van der Waals Density Functional for General Geometries [Phys. Rev. Lett. 92 , 246401 (2004)]
journal, September 2005


A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP)
journal, July 2004

  • Yanai, Takeshi; Tew, David P.; Handy, Nicholas C.
  • Chemical Physics Letters, Vol. 393, Issue 1-3, p. 51-57
  • DOI: 10.1016/j.cplett.2004.06.011

The adiabatic connection method: a non-empirical hybrid
journal, January 1997


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


Microscopic Origin of Thermal Conductivity Reduction in Disordered van der Waals Solids
journal, August 2015


Double-hybrid density functionals with long-range dispersion corrections: higher accuracy and extended applicability
journal, January 2007

  • Schwabe, Tobias; Grimme, Stefan
  • Physical Chemistry Chemical Physics, Vol. 9, Issue 26
  • DOI: 10.1039/b704725h

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

Exchange and correlation in atoms, molecules, and solids by the spin-density-functional formalism
journal, May 1976


Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections
journal, January 2008

  • Chai, Jeng-Da; Head-Gordon, Martin
  • Physical Chemistry Chemical Physics, Vol. 10, Issue 44
  • DOI: 10.1039/b810189b

Thomas-Fermi model: The second correction
journal, November 1981


Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Coupling‐constant dependence of atomization energies
journal, January 1997


Dispersion Interactions with Density-Functional Theory: Benchmarking Semiempirical and Interatomic Pairwise Corrected Density Functionals
journal, October 2011

  • Marom, Noa; Tkatchenko, Alexandre; Rossi, Mariana
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 12
  • DOI: 10.1021/ct2005616

Gaussian‐1 theory: A general procedure for prediction of molecular energies
journal, May 1989

  • Pople, John A.; Head‐Gordon, Martin; Fox, Douglas J.
  • The Journal of Chemical Physics, Vol. 90, Issue 10
  • DOI: 10.1063/1.456415

First-principles study of van der Waals interactions in MoS 2 and MoO 3
journal, July 2014


Exchange functional that tests the robustness of the plasmon description of the van der Waals density functional
journal, January 2014


Performance of the van der Waals Density Functional VV10 and (hybrid)GGA Variants for Thermochemistry and Noncovalent Interactions
journal, October 2011

  • Hujo, Waldemar; Grimme, Stefan
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 12
  • DOI: 10.1021/ct200644w

Van der Waals density functional: Self-consistent potential and the nature of the van der Waals bond
journal, September 2007


To Wet or Not to Wet? Dispersion Forces Tip the Balance for Water Ice on Metals
journal, January 2011


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

Van der Waals Density Functional for General Geometries
journal, June 2004


Perspective: Fifty years of density-functional theory in chemical physics
journal, May 2014

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 140, Issue 18
  • DOI: 10.1063/1.4869598

Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999

  • Adamo, Carlo; Barone, Vincenzo
  • The Journal of Chemical Physics, Vol. 110, Issue 13
  • DOI: 10.1063/1.478522

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

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


Ab initio pseudopotentials for electronic structure calculations of poly-atomic systems using density-functional theory
journal, June 1999


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


Van der Waals Density Functional for Layered Structures
journal, September 2003


Density functional theory with London dispersion corrections: Density functional theory with London dispersion corrections
journal, March 2011

  • Grimme, Stefan
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 1, Issue 2
  • DOI: 10.1002/wcms.30

Thermal transport in van der Waals solids from first-principles calculations
journal, September 2016


Structure and binding in crystals of cagelike molecules: Hexamine and platonic hydrocarbons
journal, April 2010

  • Berland, Kristian; Hyldgaard, Per
  • The Journal of Chemical Physics, Vol. 132, Issue 13
  • DOI: 10.1063/1.3366652

Van der Waals density functional: An appropriate exchange functional
journal, April 2010


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

Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994

  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001

van der Waals density functionals built upon the electron-gas tradition: Facing the challenge of competing interactions
journal, May 2014

  • Berland, Kristian; Arter, Calvin A.; Cooper, Valentino R.
  • The Journal of Chemical Physics, Vol. 140, Issue 18
  • DOI: 10.1063/1.4871731

Perspective on density functional theory
journal, April 2012

  • Burke, Kieron
  • The Journal of Chemical Physics, Vol. 136, Issue 15
  • DOI: 10.1063/1.4704546

Van der Waals density functionals applied to solids
journal, May 2011


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


Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988


Benchmark database of accurate (MP2 and CCSD(T) complete basis set limit) interaction energies of small model complexes, DNA base pairs, and amino acid pairs
journal, January 2006

  • Jurečka, Petr; Šponer, Jiří; Černý, Jiří
  • Physical Chemistry Chemical Physics, Vol. 8, Issue 17, p. 1985-1993
  • DOI: 10.1039/b600027d

    Works referencing / citing this record:

    Sterically controlled mechanochemistry under hydrostatic pressure
    journal, February 2018


    Push it to the limit: comparing periodic and local approaches to density functional theory for intermolecular interactions
    journal, June 2018


    Sterically controlled mechanochemistry under hydrostatic pressure
    journal, February 2018


    Push it to the limit: comparing periodic and local approaches to density functional theory for intermolecular interactions
    journal, June 2018