Skip to main content
SpringerLink
Log in

Complexes of Li, Na, and Mg with 2D allotropies of second and third period: a theoretical study

  • Original Paper
  • Published:
Journal of Molecular Modeling Aims and scope Submit manuscript

Abstract

Complexes of Li, Na, and Mg with graphene, silicene, phosphorene nanoflakes (NFs), and their 2D allotropies have been studied at dispersion corrected TPSS/def-TZVP level of theory. The energy partition analysis of the complexes revealed that for most of the complexes exchange and correlation energies represent dominant contributions to the binding with strong charge transfer from the metal atom to a NF. The exceptions are Mg complexes of graphene and phosphorene NFs where binding is due to dispersion and correlation terms. This difference is also reflected in large Mg-NF distances suggesting weak intermolecular interactions in these complexes. The calculated activation energies for metal hopping are easily achievable at room temperatures for carbon and silicon allotropies. However, they are significantly higher for phosphorus allotropies reaching almost 18 kcal/mol. Generally, activation energies for hopping increase with binding energies for graphene, silicene, and phosphorene NFs. This trend does not observe however for graphene, silicene, and phosphorene 2D allotropies.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8
Fig. 9
Fig. 10
Fig. 11
Fig. 12
Fig. 13
Fig. 14

Similar content being viewed by others

Data availability

Not applicable.

Code availability

TURBOMOLE V7.5 2020, a development of University of Karlsruhe and Forschungszentrum Karlsruhe GmbH, 1989–2007, TURBOMOLE GmbH, since 2007; available from https://www.turbomole.org.

References

  1. Novoselov KS, A K Geim, S V Morozov, et al (2004) Electric field effect in atomically thin carbon films. Science 306:666–669. https://doi.org/10.1126/science.1102896

  2. Joensen P, Frindt RF, Morrison SR (1986) Single-layer MoS2. Mater Res Bull 21:457–461. https://doi.org/10.1016/0025-5408(86)90011-5

    Article  CAS  Google Scholar 

  3. Chang H, Wu H (2013) Graphene-based nanomaterials: synthesis, properties, and optical and optoelectronic applications. Adv Func Mat 23: https://doi.org/10.1002/adfm.201202460

  4. Aufray B, Kara A, Vizzini S, et al (2010) Graphene-like silicon nanoribbons on Ag(110): A possible formation of silicene. App Phys Lett 96: https://doi.org/10.1063/1.3419932

  5. Lalmi B, Oughaddou H, Enriquez H, et al (2010) Epitaxial growth of a silicene sheet. App Phys Lett 97: https://doi.org/10.1063/1.3524215

  6. Castellanos-Gomez A (2015) Black phosphorus: narrow gap, wide applications. The Journal of Physical Chemistry Letters 6: https://doi.org/10.1021/acs.jpclett.5b01686

  7. Dávila ME, Xian L, Cahangirov S, et al (2014) Germanene: a novel two-dimensional germanium allotrope akin to graphene and silicene. New J Phys 16: https://doi.org/10.1088/1367-2630/16/9/095002

  8. Mannix AJ, Zhou X-F, Kiraly B, et al (2015) Synthesis of borophenes: anisotropic, two-dimensional boron polymorphs. Science 350: https://doi.org/10.1126/science.aad1080

  9. Feng B, Zhang J, Zhong Q, et al (2016) Experimental realization of two-dimensional boron sheets. Nat Chem 8 https://doi.org/10.1038/nchem.2491

  10. Enyashin AN, Ivanovskii AL (2011) Graphene allotropes physica status solidi (b) 248:1879–1883. https://doi.org/10.1002/pssb.201046583

    Article  CAS  Google Scholar 

  11. Chuvilin A, Meyer JC, Algara-Siller G, Kaiser U (2009) From graphene constrictions to single carbon chains. New J Phys 11:083019. https://doi.org/10.1088/1367-2630/11/8/083019

    Article  CAS  Google Scholar 

  12. de la Garza CGV, Narváez WEV, Rodríguez LDS, Fomine S (2021) Novel 2D allotropic forms and nanoflakes of silicon, phosphorus, and germanium: a computational study. J Mol Model 27:142. https://doi.org/10.1007/s00894-021-04775-4

    Article  CAS  PubMed  Google Scholar 

  13. Mpourmpakis G, Froudakis GE, Tylianakis E (2006) Haeckelites: a promising anode material for lithium batteries application. An ab initio and molecular dynamics theoretical study. Applied Physics Letters 89: https://doi.org/10.1063/1.2403922

  14. Xu Y, Wu X, Ji X (2021) The Renaissance of Proton Batteries. Small Structures 2:. https://doi.org/10.1002/sstr.202000113

  15. Slater MD, Kim D, Lee E, Johnson CS (2013) Sodium-ion batteries. Adv Func Mater 23: https://doi.org/10.1002/adfm.201200691

  16. Aurbach D, Lu Z, Schechter A, et al (2000) Prototype systems for rechargeable magnesium batteries. Nature 407: https://doi.org/10.1038/35037553

  17. Tao J, Perdew JP, Staroverov VN, Scuseria GE (2003) Climbing the density functional ladder: nonempirical meta–generalized gradient approximation designed for molecules and solids. Phys Rev Lett 91: https://doi.org/10.1103/PhysRevLett.91.146401

  18. Schäfer A, Huber C, Ahlrichs R (1994) Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr. J Chem Phys 100: https://doi.org/10.1063/1.467146

  19. Grimme S, Ehrlich S, Goerigk L (2011) Effect of the damping function in dispersion corrected density functional theory. J Comput Chem 32: https://doi.org/10.1002/jcc.21759

  20. TURBOMOLE V7.5 2020, a development of University of Karlsruhe and Forschungszentrum Karlsruhe GmbH, 1989–2007, TURBOMOLE GmbH, since 2007; available from https://www.turbomole.org

  21. Su P, Li H (2009) Energy decomposition analysis of covalent bonds and intermolecular interactions. The Journal of Chemical Physics 131: https://doi.org/10.1063/1.3159673

Download references

Funding

We acknowledge the financial support from PAPIIT (IN201219/31) and the financial support from CONACyT (Grant 251684). W.E.V.N. acknowledges support from DGAPA of the UNAM under postdoctoral fellowship Grant No. CJIC/CTIC/4732/2O2O.

Author information

Authors and Affiliations

  1. Instituto de Investigaciones en Materiales, Universidad Nacional Autónoma de México, Apartado Postal 70-360, CU, Coyoacán, DF, 04510, México

    Wilmer Esteban Vallejo Narváez, Cesar Gabriel Vera de la Garza, Luis Daniel Solís Rodríguez & Serguei Fomine

Authors
  1. Wilmer Esteban Vallejo Narváez
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Cesar Gabriel Vera de la Garza
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Luis Daniel Solís Rodríguez
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Serguei Fomine
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

Cesar Gabriel Vera de la Garza—a PhD student—performed EDA analysis.

Wilmer Esteban Vallejo Narváez—a postdoctoral fellow—transition state search, and partial manuscript writing.

Luis Daniel Solís Rodríguez—an undergraduate student—routine optimizations of complexes.

Seguei Fomine—group leader—the manuscript idea and writing.

Corresponding author

Correspondence to Serguei Fomine.

Ethics declarations

Conflict of interest

The authors declare no competing interests.

Finding

PAPIIT (IN201219/31)

CONACyT (Grant 251,684).

DGAPA of the UNAM under postdoctoral fellowship Grant No. CJIC/CTIC/4732/2O2O.

Additional information

Publisher's note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (PDF 441 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Narváez, W.E.V., de la Garza, C.G.V., Rodríguez, L.D.S. et al. Complexes of Li, Na, and Mg with 2D allotropies of second and third period: a theoretical study. J Mol Model 28, 22 (2022). https://doi.org/10.1007/s00894-021-05019-1

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s00894-021-05019-1

Keywords

Search

Navigation