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Despite differing atomic bonds, graphite and hexagonal boron nitride (h-BN) exhibit similar interlayer distances due to compensating electrostatic and dispersive forces. This finding applies to other polar layered materials.

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Area of Science:

  • Materials Science
  • Condensed Matter Physics
  • Computational Chemistry

Background:

  • Graphite and hexagonal boron nitride (h-BN) are layered materials with hexagonal lattices.
  • They possess distinct intralayer bonding (nonpolar C-C vs. polar B-N) and atomic polarizabilities.
  • Despite these differences, they show nearly identical interlayer distances.

Purpose of the Study:

  • To comparatively investigate the interlayer bonding nature in graphite and h-BN.
  • To elucidate the reasons behind their similar interlayer distances despite structural and electronic disparities.
  • To generalize findings regarding electrostatic interactions in polar layered systems.

Main Methods:

  • Full lattice sum calculations for electrostatic interactions in h-BN.
  • Analysis of higher-order electrostatic multipoles, exchange, and short-range correlation Kohn-Sham contributions.
  • Evaluation of dispersive energy terms, including C6 coefficients, and binding energy curves.

Main Results:

  • Electrostatic contributions from partially charged centers in h-BN are negligible for binding energy.
  • Kohn-Sham contributions, Pauli repulsions, and kinetic energy terms largely cancel out.
  • Dispersive energy terms, specifically the C6 coefficient, are similar for B-N and C-C interactions, leading to comparable binding.

Conclusions:

  • Interlayer binding in graphite and h-BN is dominated by similar dispersive and kinetic energy contributions, not simple electrostatic interactions.
  • The similar interlayer distances and binding energies arise from a delicate balance of various interaction types.
  • The role of electrostatic interactions in polar layered systems is less significant than previously assumed for interlayer binding.