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Title: Nature of Interlayer Binding and Stacking of sp–sp 2 Hybridized Carbon Layers: A Quantum Monte Carlo Study

Abstract

α-graphyne is a two-dimensional sheet of sp-sp2 hybridized carbon atoms in a honeycomb lattice. While the geometrical structure is similar to that of graphene, the hybridized triple bonds give rise to electronic structure that is different from that of graphene. Similar to graphene, α-graphyne can be stacked in bilayers with two stable configurations, but the different stackings have very different electronic structures: one is predicted to have gapless parabolic bands and the other a tunable bandgap which is attractive for applications. In order to realize applications, it is crucial to understand which stacking is more stable. This is difficult to model, as the stability is a result of weak interlayer van der Waals interactions which are not well captured by density functional theory (DFT). We have used quantum Monte Carlo simulations that accurately include van der Waals interactions to calculate the interlayer binding energy of bilayer graphyne and to determine its most stable stacking mode. Our results show that inter-layer bindings of sp- and sp2-bonded carbon networks are significantly underestimated in a Kohn-Sham DFT approach, even with an exchange-correlation potential corrected to include, in some approximation, van der Waals interactions. Finally, our quantum Monte Carlo calculations reveal that the interlayermore » binding energy difference between the two stacking modes is only 0.9(4) eV/atom. From this we conclude that the two stable stacking modes of bilayer α-graphyne are almost degenerate with each other, and both will occur with about the same probability at room temperature unless there is a synthesis path that prefers one stacking over the other.« less

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [1];  [3]
+ Show Author Affiliations
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Leadership Computing Facility
  2. Intel Corporation, Hillsboro, OR (United States)
  3. Konkuk Univ., Seoul (Korea). Dept. of Physics
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Material Science Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1395067
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Theory and Computation
Additional Journal Information:
Journal Volume: 13; Journal Issue: 11; Journal ID: ISSN 1549-9618
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Quantum Monte Carlo; Diffusion Monte Carlo; QMCPACK; Graphene; Graphyne; High Accuracy; First principle Calculations; ab-initio

Citation Formats

Shin, Hyeondeok, Kim, Jeongnim, Lee, Hoonkyung, Heinonen, Olle, Benali, Anouar, and Kwon, Yongkyung. Nature of Interlayer Binding and Stacking of sp–sp 2 Hybridized Carbon Layers: A Quantum Monte Carlo Study. United States: N. p., 2017. Web. doi:10.1021/acs.jctc.7b00747.
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Shin, Hyeondeok, Kim, Jeongnim, Lee, Hoonkyung, Heinonen, Olle, Benali, Anouar, & Kwon, Yongkyung. Nature of Interlayer Binding and Stacking of sp–sp 2 Hybridized Carbon Layers: A Quantum Monte Carlo Study. United States. https://doi.org/10.1021/acs.jctc.7b00747
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Shin, Hyeondeok, Kim, Jeongnim, Lee, Hoonkyung, Heinonen, Olle, Benali, Anouar, and Kwon, Yongkyung. Wed . "Nature of Interlayer Binding and Stacking of sp–sp 2 Hybridized Carbon Layers: A Quantum Monte Carlo Study". United States. https://doi.org/10.1021/acs.jctc.7b00747. https://www.osti.gov/servlets/purl/1395067.
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@article{osti_1395067,
title = {Nature of Interlayer Binding and Stacking of sp–sp 2 Hybridized Carbon Layers: A Quantum Monte Carlo Study},
author = {Shin, Hyeondeok and Kim, Jeongnim and Lee, Hoonkyung and Heinonen, Olle and Benali, Anouar and Kwon, Yongkyung},
abstractNote = {α-graphyne is a two-dimensional sheet of sp-sp2 hybridized carbon atoms in a honeycomb lattice. While the geometrical structure is similar to that of graphene, the hybridized triple bonds give rise to electronic structure that is different from that of graphene. Similar to graphene, α-graphyne can be stacked in bilayers with two stable configurations, but the different stackings have very different electronic structures: one is predicted to have gapless parabolic bands and the other a tunable bandgap which is attractive for applications. In order to realize applications, it is crucial to understand which stacking is more stable. This is difficult to model, as the stability is a result of weak interlayer van der Waals interactions which are not well captured by density functional theory (DFT). We have used quantum Monte Carlo simulations that accurately include van der Waals interactions to calculate the interlayer binding energy of bilayer graphyne and to determine its most stable stacking mode. Our results show that inter-layer bindings of sp- and sp2-bonded carbon networks are significantly underestimated in a Kohn-Sham DFT approach, even with an exchange-correlation potential corrected to include, in some approximation, van der Waals interactions. Finally, our quantum Monte Carlo calculations reveal that the interlayer binding energy difference between the two stacking modes is only 0.9(4) eV/atom. From this we conclude that the two stable stacking modes of bilayer α-graphyne are almost degenerate with each other, and both will occur with about the same probability at room temperature unless there is a synthesis path that prefers one stacking over the other.},
doi = {10.1021/acs.jctc.7b00747},
journal = {Journal of Chemical Theory and Computation},
number = 11,
volume = 13,
place = {United States},
year = {2017},
month = {10}
}
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Works referenced in this record:

Two-dimensional gas of massless Dirac fermions in graphene
journal, November 2005

  • Novoselov, K. S.; Geim, A. K.; Morozov, S. V.
  • Nature, Vol. 438, Issue 7065, p. 197-200
  • DOI: 10.1038/nature04233

Experimental observation of the quantum Hall effect and Berry's phase in graphene
journal, November 2005

  • Zhang, Yuanbo; Tan, Yan-Wen; Stormer, Horst L.
  • Nature, Vol. 438, Issue 7065, p. 201-204
  • DOI: 10.1038/nature04235

The rise of graphene
journal, March 2007

  • Geim, A. K.; Novoselov, K. S.
  • Nature Materials, Vol. 6, Issue 3, p. 183-191
  • DOI: 10.1038/nmat1849

Graphene: Status and Prospects
journal, June 2009

Electronic Properties of Bilayer Graphene Strongly Coupled to Interlayer Stacking and an External Electric Field
journal, July 2015

Controlling the Electronic Structure of Bilayer Graphene
journal, August 2006

Biased Bilayer Graphene: Semiconductor with a Gap Tunable by the Electric Field Effect
journal, November 2007

Gate-induced insulating state in bilayer graphene devices
journal, December 2007

  • Oostinga, Jeroen B.; Heersche, Hubert B.; Liu, Xinglan
  • Nature Materials, Vol. 7, Issue 2
  • DOI: 10.1038/nmat2082

Formation of Bilayer Bernal Graphene: Layer-by-Layer Epitaxy via Chemical Vapor Deposition
journal, March 2011

  • Yan, Kai; Peng, Hailin; Zhou, Yu
  • Nano Letters, Vol. 11, Issue 3
  • DOI: 10.1021/nl104000b

Structure‐property predictions for new planar forms of carbon: Layered phases containing s p 2 and s p atoms
journal, December 1987

  • Baughman, R. H.; Eckhardt, H.; Kertesz, M.
  • The Journal of Chemical Physics, Vol. 87, Issue 11
  • DOI: 10.1063/1.453405

Families of carbon nanotubes: Graphyne-based nanotubes
journal, July 2003

New families of carbon nanotubes based on graphyne motifs
journal, January 2004

High Mobility and High Storage Capacity of Lithium in sp–sp 2 Hybridized Carbon Network: The Case of Graphyne
journal, April 2011

  • Zhang, Hongyu; Zhao, Mingwen; He, Xiujie
  • The Journal of Physical Chemistry C, Vol. 115, Issue 17
  • DOI: 10.1021/jp201062m

Graphyne and Graphdiyne: Promising Materials for Nanoelectronics and Energy Storage Applications
journal, February 2012

  • Srinivasu, K.; Ghosh, Swapan K.
  • The Journal of Physical Chemistry C, Vol. 116, Issue 9
  • DOI: 10.1021/jp212181h

Competition for Graphene: Graphynes with Direction-Dependent Dirac Cones
journal, February 2012

Graphyne: Hexagonal network of carbon with versatile Dirac cones
journal, September 2012

Thermodynamically Stable Calcium-Decorated Graphyne as a Hydrogen Storage Medium
journal, September 2012

  • Hwang, Ho Jun; Kwon, Yongkyung; Lee, Hoonkyung
  • The Journal of Physical Chemistry C, Vol. 116, Issue 38
  • DOI: 10.1021/jp306222v

Carrier Mobility in Graphyne Should Be Even Larger than That in Graphene: A Theoretical Prediction
journal, April 2013

  • Chen, Jianming; Xi, Jinyang; Wang, Dong
  • The Journal of Physical Chemistry Letters, Vol. 4, Issue 9
  • DOI: 10.1021/jz4005587

Multilayer Graphynes for Lithium Ion Battery Anode
journal, March 2013

  • Hwang, Ho Jun; Koo, Jahyun; Park, Minwoo
  • The Journal of Physical Chemistry C, Vol. 117, Issue 14
  • DOI: 10.1021/jp3105198

Tunable double Dirac cone spectrum in bilayer α-graphyne
journal, July 2013

  • Leenaerts, O.; Partoens, B.; Peeters, F. M.
  • Applied Physics Letters, Vol. 103, Issue 1
  • DOI: 10.1063/1.4812977

Raman Spectrum of Graphene and Graphene Layers
journal, October 2006

Energy gaps, magnetism, and electric-field effects in bilayer graphene nanoribbons
journal, July 2008

Excitonic Effects on the Optical Response of Graphene and Bilayer Graphene
journal, October 2009

Ab initio study of gap opening and screening effects in gated bilayer graphene
journal, April 2009

Van Der Waals Density Functionals for Graphene Layers and Graphite
journal, November 2011

Ab initio studies of hydrogen adatoms on bilayer graphene
journal, May 2012

Accurate description of van der Waals complexes by density functional theory including empirical corrections
journal, January 2004

  • Grimme, Stefan
  • Journal of Computational Chemistry, Vol. 25, Issue 12
  • DOI: 10.1002/jcc.20078

Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006

  • Grimme, Stefan
  • Journal of Computational Chemistry, Vol. 27, Issue 15, p. 1787-1799
  • DOI: 10.1002/jcc.20495

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

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

Interlayer interaction and relative vibrations of bilayer graphene
journal, January 2011

  • Lebedeva, Irina V.; Knizhnik, Andrey A.; Popov, Andrey M.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 13
  • DOI: 10.1039/c0cp02614j

van der Waals Interactions between Thin Metallic Wires and Layers
journal, October 2007

Nature and Strength of Interlayer Binding in Graphite
journal, November 2009

Application of Diffusion Monte Carlo to Materials Dominated by van der Waals Interactions
journal, June 2014

  • Benali, Anouar; Shulenburger, Luke; Romero, Nichols A.
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 8
  • DOI: 10.1021/ct5003225

Binding and Diffusion of Lithium in Graphite: Quantum Monte Carlo Benchmarks and Validation of van der Waals Density Functional Methods
journal, November 2014

  • Ganesh, P.; Kim, Jeongnim; Park, Changwon
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 12
  • DOI: 10.1021/ct500617z

Van der Waals interaction in a boron nitride bilayer
journal, November 2014

Quantum Monte Carlo Calculation of the Binding Energy of Bilayer Graphene
journal, September 2015

The Nature of the Interlayer Interaction in Bulk and Few-Layer Phosphorus
journal, November 2015

Quantum Monte Carlo simulations of solids
journal, January 2001

Fixed‐node quantum Monte Carlo for molecules a) b)
journal, December 1982

  • Reynolds, Peter J.; Ceperley, David M.; Alder, Berni J.
  • The Journal of Chemical Physics, Vol. 77, Issue 11
  • DOI: 10.1063/1.443766

Hybrid algorithms in quantum Monte Carlo
journal, December 2012

Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

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

Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

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

Energy-consistent pseudopotentials for quantum Monte Carlo calculations
journal, June 2007

  • Burkatzki, M.; Filippi, C.; Dolg, M.
  • The Journal of Chemical Physics, Vol. 126, Issue 23
  • DOI: 10.1063/1.2741534

Energy-consistent small-core pseudopotentials for 3d-transition metals adapted to quantum Monte Carlo calculations
journal, October 2008

  • Burkatzki, M.; Filippi, Claudia; Dolg, M.
  • The Journal of Chemical Physics, Vol. 129, Issue 16
  • DOI: 10.1063/1.2987872

Cohesion energetics of carbon allotropes: Quantum Monte Carlo study
journal, March 2014

  • Shin, Hyeondeok; Kang, Sinabro; Koo, Jahyun
  • The Journal of Chemical Physics, Vol. 140, Issue 11
  • DOI: 10.1063/1.4867544

Beyond the locality approximation in the standard diffusion Monte Carlo method
journal, October 2006

Size Dependence in the Stabilities and Electronic Properties of α-Graphyne and Its Boron Nitride Analogue
journal, January 2013

  • Özçelik, V. Ongun; Ciraci, S.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 5
  • DOI: 10.1021/jp3111869

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

Nonlocal van der Waals density functional made simple and efficient
journal, January 2013

A density‐functional study of the intermolecular interactions of benzene
journal, November 1996

  • Meijer, Evert Jan; Sprik, Michiel
  • The Journal of Chemical Physics, Vol. 105, Issue 19
  • DOI: 10.1063/1.472649
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    journal, January 2018

    • Yun, Jiangni; Zhang, Yanni; Ren, Yanbing
    • Physical Chemistry Chemical Physics, Vol. 20, Issue 42
    • DOI: 10.1039/c8cp03533d

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    journal, August 2019

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    journal, June 2018

    • Kadioglu, Yelda; Santana, Juan A.; Özaydin, H. Duygu
    • The Journal of Chemical Physics, Vol. 148, Issue 21
    • DOI: 10.1063/1.5026120

    Investigation on probing explosive nitroaromatic compound vapors using graphyne nanosheet: a first-principle study
    journal, November 2018

    Tunable electric properties of bilayer InSe with different interlayer distances and external electric field
    journal, February 2018

    • Shang, Jimin; Pan, Longfei; Wang, Xiaoting
    • Semiconductor Science and Technology, Vol. 33, Issue 3
    • DOI: 10.1088/1361-6641/aaaad2

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