In this exercise the vibrational modes (phonon modes) of MgO will be computed. The phonon modes will be displayed as dispersion curves, a density of states and animated.

In a later exercise the free energy will be computed within the harmonic approximation. For this an accurate phonon density of states must be computed.

In order to visualise the phonon modes and understand the variation
of frequencies with **k** compute the phonon frequencies along a
path in **k**-space. These are the *w _{j,k}* curves
that will also be discussed in a Lecture -
Vibrations in crystals

The essential point is that *every possible vibration* of the crystal can be
labelled with a **k**-vector which is related to the direction and
wavelength of the vibration.

The calculation is performed as follows;

Load the MgO structure and bring up the

Execute GULPpanel.Click on

General optsand selectPhonon Dispersion.Set Npoints to 50

Ensure that

Calculate Phonon Eigenvectorsis selected.

The special points along the conventional path in **k**-space,
W-L-G-W-X-K, are displayed at the bottom of the panel. The phonons will
be computed at 50 points along this path. Note that the path and the
names for the particular end points are simply a widely used convention
which allows researchers to display phonon frequencies easily - it is
difficult to display the variation of the frequency over the full 3D
**k**-space.

RunGULP andRecover Files

A window containing the Log File will pop up.

In addition a window **1D Data Display** will pop up.

The phonon dispersion curves should be available for plotting.

Select

GULP phonon dispersionin the1D Data Displaypanel.Click on the

Draw 1D databutton

The **2DView** window will pop up and should contain the
*phonon dispersion curves* looking something like this.

At this point you will have developed a keen understanding of why many researchers invest in 19 inch monitors - if you close windows that you are not currently using it will help to keep the screen tidy :-).

Display -> Animate -> Property

The **Create Property Animation** panel will pop up listing all of
the phonon modes computed for the dispersion plot.

Select one of the phonon modes - mode 117 is a good one to start with (the mode numbers are in brackets after the frequency and k-point).

Set **N frames** to, say, 30 and **max amplitude** to 0.2 and
click **Apply**.

The **Animate Model** panel should pop up. Set **Cycle Options**
to **Cycle** and click **Run** to animate the selected phonon.
DLV will automatically switch to a suitable supercell which wholly
contains the phonon being animated (ie: a cell in which the vibrating
atoms repeat once). Mode 117 is at the **k**-point (0.0, 0.0, 0.0) and
so can be represented within the primitive unit cell.

In the 3DView window the atoms begin to vibrate - this is the motion associated with the mode you have selected.

Note: DLV scales (normalises) the image every time it is refreshed which
may cause the animation to jump around a little - you can prevent this by
turning off the **Auto Normalise** option on the main control panel.

Note that you can examine the phonons at all of the 50 k-points we
have computed for the dispersion curve. All of the possible vibrations
of the infinite lattice of Mg and O ions can be computed and visualised
in this way - we simply need to compute at enough **k**-points.

In order to compute, for example, a free energy a sum over **all**
of the vibrations of the lattice is required - that means a sum over all
possible **k**-points. In the computer this must
be approximated by a sum over a large but finite number of points on a grid.
In practical work the question is - how many points are required to obtain
an accurate answer ?

The *density of states* is a useful object which summarises the
dispersion curves - it is an *average* over all **k**-points yielding
the number of vibrational modes at each frequency (the density of modes).

A calculation is performed as follows.

Load an MgO structure and bring up the

Execute GULPpanel.Click on

General optsand selectPhonon DOS..The

shrinking factorsalong theA,BandCdirections will be displayed; these simply define the grid ofk-points on which the average will be performed and default to a simgle point - a 1x1x1 grid.

The panel should look like this;

Click on

Run GULPand after completionRecover Files

A window containing the Log File will pop up.

In addition a window **1D Data Display** will pop up.

The phonon density of states should be available for plotting.

Select

GULP phonon Density of Statesin the1D Data Displaypanel.Click on the

Draw 1D databutton

The **2DView** window will pop up and should contain a density
of states looking something like this.

This is the density of states (DOS) computed from a single
**k**-point - not much of an average ! It consists of 4 distinct peaks.

In order to obtain a smooth curve the phonons must be sampled
on a denser grid of **k**-points.

In order to use more **k** points rerun the the density
of states calculation increasing the shrinking factors from
1x1x1.

Try 2x2x2, 3x3x3, 4x4x4 etc. grids and see how the density of states varies.

- The density of states for 1x1x1 grid was computed for
a single
**k**-point.

Can you work out which**k**-point by examining the dispersion curves ? look in the Log File to check.

- How does the density of states vary with grid size ?
- As the grid size increases more and more of the possible vibrations are sampled and more features appear - which grid size is the minimum for a reasonable approximation to the density of states ?
- How does the density of states computed at this optimal grid size compare to that computed for smaller and larger grids ?
- How is the density of states related to the dispersion curves ?

- Would this optimal grid size for MgO be appropriate for a calculation on;
- a similar oxide (eg: CaO) ?
- a Zeolite (eg: Faujasite) ?
- a metal (eg: lithium) ?