cohesive energy can be very instructive in understand why a particular structure It is the energy which

is needed to separate a solid into isolated, neutral atoms.Cohesive energies of solid elements typically
range between 1 and 10 eV/atom except for the noble gases which have smaller cohesive energies [1].
The cohesive energy represents a measure for the bonding strength in a solid and can be used, for
instance, to identify the equilibrium structure of a crystal at low temperature, since the structure with
the highest cohesive energy will be adopted.In this case study, DFT (density functional theory)
calculations on the cohesive energy of magnesium (Mg) will be presented. The calculations have been
performed using the ABINIT [2] module of Scienomics MAPS platform [3]. In the first part, we will
demonstrate the validation of the parameter set for the DFT calculations. In the second part, the
results of the cohesive energy calculations for the experimental and geometry optimized structure of the
Mg unit cell will be discussed.

Convergence of energy cutoff and the number of k-points

In electronic structures calculations of solids, the energy cutoff and the number of k-points in the
Brillouin zone are two important parameters which have to be selected very carefully. Best practices in
this field usually demand a convergence study of the quantity of interest with respect to these
parameters prior to production runs. Therefore, the convergence of the total energy with respect to the
energy cutoff and the number of k-points has been checked. For this purpose, the total energy of the
Mg unit cell has been calculated and the energy cutoff and number of k-points, respectively, have been
systematically increased. The generalized gradient approximation (GGA) was used together with the
Perdew-Burke-Ernzerhof (PBE) density functional and the respective PAW (Projector Augmented-
Wave) pseudopotential generated by AtomPAW [4] as shipped with MAPS/ABINIT. The structure of the
Mg unit cell has been taken from MAPS structure library. The cell lengths of this structure are a =
3.201 Å and c = 5.210 Å which corresponds to the experimental values.

The results of the convergence study are illustrated in Figure 1 and 2. Figure 1 shows the convergence
of the total energy with respect to the energy cutoff. Convergence is reached with an energy cutoff of
1000 eV providing an accuracy of the absolute energy of better than 0.001 eV (0.1 kJ/mol).

c16-f1-mg-convergence-in-ecutoff
Figure 1: Convergence of the total energy of Mg with respect to the energy cutoff. The convergence
behavior of the total energy with respect to the number of k-points is depicted in Figure 2. An accuracy
of the absolute energy of better than 0.001 eV (0.1 kJ/mol) is achieved when using a 8x8x8 k-point
mesh.
c16-f2-convergence-in-k-points
Figure 2: Convergence of the total energy of Mg with respect to the number of k-points.
Calculation of the cohesive energy

For calculating the cohesive energy, the total energy of the bulk and of a free atom is required. The
total energy of the bulk has been calculated using the GGA approach together with the GGA-PAW
pseudopotential generated by Holzwarth using AtomPAW [4] as shipped with MAPS/ABINIT. Based on
the above discussed convergence study, the energy cutoff has been set to 1000 eV and a 8x8x8 k-point
grid was used for Brillouin zone integration.

In order to calculated the energy of the isolated Mg atom, MAPS crystal builder (see Figure 3) has
been used to place a single Mg atom into a cubic box with a cell length of a = b = c = 10 Å.
Figure 3: MAPS interface showing the unit cells of the bulk and the isolated atom, respectively, and
MAPS Crystal builder. The total energy of the free atom has then been obtained from a calculation at
the G point using the same energy cutoff as chosen for the bulk (1000 eV).
Figure 3: MAPS interface showing the unit cells of the bulk and the isolated atom, respectively, and
MAPS Crystal builder.
The total energy of the free atom has then been obtained from a calculation at the G point using the
same energy cutoff as chosen for the bulk (1000 eV).