Application Note

Q.

Cohesive Energy of Diamond

The cohesive energy of a solid is defined as the energy required for separating the condensed
material into isolated free atoms. Cohesive energies range from about 0.1 eV or 10 kJ/mol for inert
gases up to about 8 eV or 800 kJ/mol per atom for strongly bound materials such as diamond or
tungsten. The calculation of the cohesive energy requires a value of the total energy for the solid
and of the free atoms. The energy difference between atoms and a solid is a measure of the
bonding strength in the solid material. This appears to be a straightforward task. In practice,
however, there are a number of subtleties, which are illustrated here for the case of a seemingly
simple system, namely diamond.

Outline of Approach
In principle, the approach is very simple. One needs to compute the total energy of diamond
and of an isolated C atom. The energy difference per atom is the cohesive energy. Now let us
go through this process very carefully.
1. Get Structure

A search in the crystallographic databases with INFOMATICA gives a number of structures,

most of them measured at room temperature. For simplicity, lets take the first entry, which
is ICSD.66464 with a reported lattice parameter of a= 3.5667 .
2. Select Hamiltonian

The Purdue-Burke-Ernzerhof form of the generalized gradient approximation is currently a

widely used approach to treat exchange and correlation effects in electronic structure
calculations. We follow this approach, but we should be aware that this is one particular
choice. Diamond is non-magnetic, so we can use a non-spin-polarized Hamiltonian.
Furthermore, the atom is relatively light and relativistic spin-orbit effects can be neglected.
For the case of the free C atom, the valence states have an electronic configuration of s2p2.
There are unpaired electrons, so we need to perform the calculations for the atom with a
spin-polarized Hamiltonian. Actually, atoms are more complicated and we will come back to
this later.
3. Optimize VASP Parameters

It is well known that the total electronic energy converges rather slowly with the number of
plane waves, i.e. with the cut-off energy in the basis-set expansion. The other major
parameter in electronic structure calculations on solids is the number of k-points in the
Brillouin zone, which determines the accuracy of the charge density and the potential.

MEDEA 2.0 offers a new capability to check the convergence of the total energy with respect
to these parameters in an automated way. To this end, activate the window with the diamond
structure and invoke ToolsAutomated Convergence from the M EDE A tool bar. Choose
Total Energy as convergence criterion and set the threshold at the rather stringent value
of 0.0001 eV. In the V ASP settings, choose Normal as precision.
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Materials Design Application Note

Cohesive Energy of Diamond

Launch the convergence calculations and use the ConvergenceMonitor to follow the
convergence of the total energy with respect to the plane-wave cut-off and the k-mesh.
In the present case, a rather large plane-wave cut-off of 938 eV and a k-mesh density of 0.18
-1 corresponding to a 17x17x17 Monkhorst-Pack mesh are needed to achieve a convergence
of the total energy of less than 0.0001 eV.
As can be seen from a plot of the total energy vs. the plane wave cut-off, the default value of
400 eV gives a total energy, which is actually very close to the converged value. However, the
convergence is not monotonic. At lower values, the total energy increases and then

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Materials Design Application Note

Cohesive Energy of Diamond

diminishes gently for higher plane wave cut-off values.

Convergence of Total Energy of Diamond

-18.17

EVASP (eV)

-18.18
-18.19
-18.20
-18.21
-18.22
300

400

500

600

700

800

900

1000

Energy cutoff (eV)

4. Compute Lattice Parameters and Total Energies

Choose the diamond structure ICSD.66464 and use the following parameters for V ASP 4.6:
Structure optimization with all three boxes checked; geometry convergence 0.01 eV/,
Accurate precision, k-mesh spacing 0.18 -1, and Tetrahedron with Blchl corrections
as integration scheme. Leave the plane wave cut-off at 400 eV.
Then launch the calculations. The resulting lattice parameter is a=3.5623 , which is 0.1 %
smaller than the experimental value used as input. The correspond total energy is
= 18.186940 eV per C2

(2-1)

The value corresponds to a unit cell with 2 carbon atoms.

If we load the optimized structure from the JobServers database and run a single-point
energy with exactly the same parameters as in the previous lattice optimization, the total
energy is
(2-2)
= 18.186157 eV per C2
The two values are slightly different, because the single point energy uses a slightly different
number of plane waves and Fourier meshes. The reason is that in an optimization of the
lattice parameter, the meshes in reciprocal space are constructed from the dimensions of the
input structure. Therefore, it is important to recompute the total energy after geometry
optimizations to ensure consistency with subsequent calculations, where, for example, only
internal parameters, such atomic positions in fractional coordinates, are optimized.
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Materials Design Application Note

Cohesive Energy of Diamond

The energy E VASP has a peculiar reference: EVASP is relative to the total energy of a spherical
atom, computed with a non-spin-polarized Hamiltonian. Therefore, E VASP is not the total
electronic energy of the system. In fact, this value would be much larger in magnitude.

To obtain a cohesive energy, we need the energy of an individual carbon atom. This is done in
the next step.
5. Compute Energy of Carbon Atom

In MEDEA, use FileNew to create a supercell for a C atom. Use EditCell to set the cell
parameters at a=10 , b=11 , and c=12 . Add a C atom at (0,0,0). Launch a V ASP singlepoint energy calculation with Accurate precision, a k-spacing of 1, i.e. use only the kpoint. Set the k-integration to Methfessel-Paxton. The total energy is
(C,non-spin-polarized) = 0.154091 eV

(2-3)

An inspection of the OUTCAR.out file shows the following occupation of the electronic levels
at the -point (which is the only k-point used here):

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Materials Design Application Note

k-point 1
band No.
1
2
3
4
5
6

Cohesive Energy of Diamond

:
0.0000
0.0000
0.0000
band energies
occupation
-13.6874
2.00000
-5.2097
0.66756
-5.2097
0.66741
-5.2094
0.66503
-0.3463
0.00000
0.7552
0.00000

The level of 13.6874 eV is the C-2s state, occupied with 2 electrons. The states # 2-4 are the
C-2p levels. Each of them is occupied with 2/3 of an electron. This makes the atom spherical
and represents an average configuration.

Now rerun the same calculation with a spin-polarized Hamiltonian. The total energy drops by
1.16 eV (or 112 kJ/mol) to
(C,spin-polarized) = 1.315324 eV

Now the occupation of the electronic levels is as follows:

spin

band No. band energies

1
-14.5784
2
-6.0199
3
-6.0189
4
-6.0140
5
-0.3973
6
0.6728
7
0.7098

occupation
1.00000
0.67576
0.67171
0.65253
0.00000
0.00000
0.00000

spin

band No. band energies

1
-11.8155
2
-3.5636
3
-3.5206
4
-3.5116
5
-0.0429
6
0.9993
7
1.0536

(2-4)

occupation
1.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000

In the C-2s states, one level is occupied with an electron with spin and one with spin . In
the 2p-states, the computational approach occupies all three -spin states with 2/3 of an
electron. The corresponding 2p states with -spin are empty. This amounts to a total of 2
unpaired electrons or a triplet state.

Spin-density functional theory predicts indeed the correct spin state of a C atom in its ground
state. However, the electronic structure of a C atom is more complicated, since the coupling
of the angular moments of the p-electrons leads to several configurations. The figure below
shows the correspondence between density functional calculations and results from HartreeFock and configuration interaction results. 1

Weinert, M, Wimmer, E and Freeman, A J. Phys Rev B. 1982, Vol. 26, p. 4571.

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Materials Design Application Note

Cohesive Energy of Diamond

Carbon Atom 1s22s22p2

Local Density
non-spin-polarized

LD 3P

spin-polarized

Hartree-Fock

1.20
1.25

average of
configurations

0.7

restricted

2.2

multiconfiguration

0.8

spin-polarized

3P

The important point here is that the electronic energy obtained from standard density
functional calculations on atoms is an average over configurations, and can differ from the
energy of the electronic ground state of that atom by several hundreds of kJ/mol. Therefore,
one needs to be really careful in making statements about the absolute value of cohesive
energies. For closed-shell atoms such as Mg, the DFT calculations come close in describing
the electronic ground state of that atom. In open shell systems, in particular transition
metals, rare earth, and actinide atoms, the difference between the electronic ground state
and the DFT results can be very large on the scale of chemical energies. Reference to spinpolarized atoms remedies some of these discrepancies, but multiplet splittings can play an
important role.
6. Compute Cohesive Energy

With these warnings in mind, let us compute a cohesive energy of diamond. From the results
of steps I.Q.4 Compute Lattice Parameters and Total Energies and I.Q.5 Compute Energy of
Carbon Atom, we obtain
cohesive(diamond) = (Catom ) (Cbulk)
eV
18.1862 eV
eV
= 1.3153
+
= 7.78
= 750.7 kJ/mol
atom
2
atom
atom

(2-5)

The experimental value for the cohesive energy of diamond is 7.37 eV, compared with our
calculated value of 7.78 eV. It is quite possible that the major source for this deviation comes
from the present DFT calculations of the C atom rather than the solid.

Copyright Materials Design, Inc. 2002-2008