Should grain-boundary energies in CSL bicrystals be computed at fixed in-plane cell vectors or after in-plane stress relaxation?

I am calculating grain-boundary energies for CSL bicrystals in Al using LAMMPS.

Geometry:

  • single GB cell
  • periodic in the GB plane: x and y
  • non-periodic/shrink-wrapped normal direction: z
  • triclinic/monoclinic box with xy tilt
  • EAM Al potential
  • GB energy calculated as excess energy, with surface-energy subtraction

I am aiming to obtain stress-free grain-boundary structures. After atomic relaxation, many GBs show residual in-plane compressive stresses. I tried using:

fix br all box/relax x 0.0 y 0.0 xy 0.0 couple none

to reduce this pressure, but for most grain boundaries, especially highly tilted ones, the pressure is not reducing as expected. Many highly tilted GBs also give:

WARNING: Triclinic box skew is large. LAMMPS will run inefficiently. (../domain.cpp:221)

My question is conceptual and practical:

Is using in-plane box/relax appropriate for grain-boundary energy calculations where the in-plane CSL-periodic cell vectors define the boundary-plane periodicity?

My concern is that relaxing x, y, and xy may elastically strain the bulk grains. Since the GB energy is referenced to a perfect unstrained bulk cohesive energy, this strain contribution may contaminate the total excess energy.

Is this concern valid? Should the in-plane CSL cell vectors normally be kept fixed for GB energy calculations, with only atomic relaxation performed, or is controlled in-plane box/relax acceptable if the surface reference cells are relaxed in the same way?

Any advice on best practice for this setup would be very helpful.

Note: This response was generated with the assistance of an AI tool (Claude) after this thread received no replies from other community members for over a week. AI-generated responses carry a real risk of error, particularly for narrow, domain-specific physics questions like this one. The methodology advice below is based on published literature, but please treat it as a starting point, not authoritative guidance, and validate against the primary references. We encourage human experts to correct or supplement this response.


On the core methodology question:

The standard approach in published large-scale atomistic grain boundary (GB) surveys (e.g., Olmsted, Foiles & Holm, Acta Materialia 57, 3694–3703, 2009; Tschopp & McDowell, Phil. Mag. 87, 3147–3173, 2007; Spearot & McDowell, JOM 2009) is to keep in-plane cell vectors fixed at the CSL-commensurate dimensions and relax only the atomic positions (and optionally the cell dimension in the normal/z direction). The key reason is thermodynamic consistency: the GB energy is defined as:

γ = (E_bicrystal − N · ε_bulk) / (2A)
where ε_bulk must be the energy per atom of a perfect crystal at the same in-plane lattice parameter as the bicrystal cell. If your bicrystal has a slight in-plane elastic strain due to the CSL construction, the reference single-crystal cells must be strained identically. Under this condition, the excess energy is dominated by the GB structural contribution and the bulk elastic artifact largely cancels.

Is in-plane box/relax ever appropriate?

Yes, with an important caveat: if you use fix box/relax x y xy to allow the in-plane dimensions to find a stress-free state, you must compute the reference single-crystal energy at those same relaxed in-plane dimensions (i.e., run the same box/relax on a pure single-crystal cell). Only then do the bulk elastic contributions cancel and you recover a physically meaningful GB energy. In practice this is rarely done in the published GB database literature, partly because it complicates the reference calculation and partly because for low- and moderate-Σ boundaries the residual in-plane elastic strain is tiny.

For high-angle, high-Σ tilt boundaries with large monoclinic xy tilt, residual in-plane compressive stress is a known issue. The standard workarounds in the literature are:

  1. Accept the fixed-cell convention and note that any residual in-plane stress contributes a small, nearly-identical elastic energy to both the bicrystal and the reference cells, so it largely cancels in the excess.
  2. Increase the GB-normal (z) dimension so the grains are thick enough that their core is elastically relaxed away from the GB; the in-plane stress is then genuinely confined to the boundary region and does not contaminate the bulk reference.
  3. Use a different supercell construction (e.g., rotating the periodic vectors so the xy tilt factor stays within LAMMPS’s |xy| ≤ 0.5·lx limit). This is what the warning about large triclinic skew is pointing to — LAMMPS is telling you that the simulation cell geometry is outside its efficient operating range.

On the large-skew LAMMPS warning:

LAMMPS requires |xy| ≤ 0.5·lx (and analogously for xz, yz). When fix box/relax changes lx and ly, the ratio xy/lx can exceed this bound, triggering the warning and eventually an error. The fix is either (a) to avoid box/relax on the in-plane dimensions for highly tilted cells, or (b) to choose a supercell with periodic vectors that have smaller tilt (many GB-construction tools, e.g. GBCode) offer this option).

Recommended references:

  • D.L. Olmsted, S.M. Foiles, E.A. Holm, “Survey of computed grain boundary properties in face-centered cubic metals: I. Grain boundary energy,” Acta Mater. 57, 3694 (2009). [link] — The canonical large GB database for FCC metals; fixed in-plane methodology.
  • M.A. Tschopp, G.J. Tucker, D.L. McDowell, “Structure and free volume of <110> symmetric tilt grain boundaries with the E structural unit,” Acta Mater. 55, 3959 (2007). — Al/Cu tilt GBs with explicit description of the fixed-cell approach.
  • H.S. Seung, D.R. Nelson, “Defects in flexible membranes with crystalline order,” Phys. Rev. A 38, 1005 (1988); and more practically, Ratanaphan et al., Acta Mater. 80, 96 (2014), “Grain boundary energies in body-centered cubic metals.” [link]
  • Tschopp & McDowell 2015 (symmetric/asymmetric tilt GBs in Cu and Al, transferability to other FCC metals): [link]
  • LAMMPS documentation for fix box/relax and triclinic box handling.