Ionic Relaxation in This allows for employing classical mechanics

DFT instead of quantum mechanics as the nuclei rather

behave like a point particle. The force acting on the
Simulation of Semiconductor Properties
I-th nuclei can then be expressed as
When simulating quantum systems, often single ∂U
𝑭𝐼 = − .
atoms are placed by hand in specified positions. ∂𝑹𝐼
The resulting constellation does not necessarily The potential 𝑈(𝑹1 , … , 𝑹𝑀 ) can be thought of a so-
represent a stable system, as the atoms influence called potential energy surface as depicted in fig.2.
one another, which could cause them to move. To
achieve a stable system, the equilibrium positions
of these atoms, hence the positions where all forces
on every particle vanish completely, have to be
computed. When using density functional theory,
the equilibrium is first found for the electrons for
specific nucleus constellation via the self-
consistent loop. After convergence, the nuclei of
the atoms might still experience forces, either of
repelling nature from the other nuclei or of
attracting nature from the electrons. If these forces
are still present, the system is in need of finding
new positions for the nuclei, in other words the Figure 2: Potential energy surface.
system has to be relaxed.
The goal is to find the positions 𝑹1 … 𝑹𝑀 such that
Mathematical Foundation the energy is at a minimum or in other words the
forces vanish.
Searching for an atomic constellation where all
In general, this can be regarded as an optimization
forces vanish, can also be thought of as searching
problem for which reason this procedure is often
for a global minimum for the energy of the system.
also called geometry optimization.
The overall potential of the nuclei can be expressed
By adjusting the positions of the atoms, a global
as
1 𝑍𝐼 𝑍𝐽 minimum for the energy can be found.
𝑈(𝑹1 , … , 𝑹𝑀 ) = ∑ + 𝐸(𝑹1 … 𝑹𝑀 ), This, however, is not always trivial, especially
2 |𝑅𝐼 − 𝑅𝐽 | when the energy function has local minima as well.
𝐼≠𝐽
where 𝐸(𝑹1 … 𝑹𝑀 ) is the total energy of the In a local minimum, the gradient (forces) would
electrons when the nuclei are held in place in the vanish, even though the global minimum is not
positions 𝑹1 … 𝑹𝑀 . reached yet. Therefore, optimization is a very
Another simplification can be achieved by taking a demanding task, for which a lot of approaches have
look at the quantum mechanical behavior of nuclei. been developed.
When looking at fig. 1, it can be noticed that the
wave function of the nucleus is very localized Optimization Algorithms
compared to the one of the electron. There exist several different optimization
algorithms, for ionic relaxation mainly steepest
descent and conjugate gradients are being used as
an approach for finding the equilibrium
constellation. Quantum Espresso for example
mainly uses a Quasi-Newton method. The
commercially available software VASP uses a
Quasi-Newton approach, however of different
type, when compared to Quantum Espresso. VASP
features a conjugate gradient method as well.
Figure 1: Ground state wave functions of an electron and nucleus
in a parabolic potential.
1
Another approach for finding the equilibrium of a
quantum system is called Damped Molecular
Dynamics. In this approach the forces for each
particle are calculated individually. The resulting
changes in positions can be calculated via
Newton’s equation of motion
𝑑 2 𝑹𝑰
𝑀 = 𝑭𝑰
𝑑𝑡 2
In order to reach an energy minimum, an additional
friction term is added, which leads to the following
equation:
𝑑 2 𝑹𝑰 2𝑀 𝑑𝑹𝑰
𝑀 2
= 𝑭𝑰 − . conv_thr = 1.d-7
𝑑𝑡 𝜏 𝑑𝑡
This equation can be solved numerically for the
positions by employing the so called Verlet
algorithm.
Both VASP and Quantum Espresso feature this
method.
Integration in the DFT Algorithm
After computing a relaxed system, the solutions for
the wave functions of the electrons might have to
be adapted due to the changed positions of the
nuclei. Therefore, the self-consistent loop of the
DFT is entered once again. Now, the wave
functions are being updated based on the new
positions of the atoms. This procedure is shown as
a flow graph in fig.3:
Figure 3: Flow graph for ionic relaxation.
Example in Quantum Espresso
In Quantum Espresso the relaxed structure can be
calculated by modifying the input file. A
corresponding input file could be the following:
&control
calculation = ’relax',
nstep=50,
etot_conv_thr = 1.d-4
forc_conv_thr = 1.d-3
...
/
...
&electrons
...
/
&ions
ion_dynamics = "bfgs"
pot_extrapolation = "second_order",
wfc_extrapolation = "second_order",
upscale = 100,
/
...
Figure 4: Example input file for Quantum Espresso to compute
relaxed structure.
The parameter calculation is specified as relax,
which indicates the computation of the relaxed
system. The next line specifies the number of
iterations for the structural optimization with the
parameter nstep. After that, the different
convergence thresholds for the energy and forces
are defined. If the total energy of the system
changes less than the value specified in
etot_conv_thr and the overall forces are smaller
than the value specified in forc_conv_thr the
algorithm terminates. After the convergence
threshold for the self-consistent loop is set by
conv_thr, the optimization algorithm is specified
with the parameter ion_dynamics. In this example
it is set to bfgs which indicates the use of the BFGS
Quasi-Newton algorithm. If set to damp, Quantum
Espresso uses the previously mentioned Damped
Molecular Dynamics method to find an
equilibrium.