Danny Rehn

        

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Phonon Calculations via VASP

Contents

Prerequisites

Before starting, you will want the following software:

  1. VASP 5.3 or greater (requires a license)
  2. Phonopy (see this link for download instructions)
  3. Access to materialsproject.com
  4. VESTA (not entirely necessary, but useful for mode visualizations)

Overview

The Phonopy Python package provides a simple interface for extracting vibrational and thermal properties of materials from VASP output. This tutorial shows how to use VASP and Phonopy for phonon density of states, dispersion, and free energy calculations. We will use bulknn MoS\(_2\) as an example. In general, phonon calculations with VASP involve the following steps:

  1. Relaxation of the atomic positions and/or cell
  2. Checking atomic positions/lattice constants to ensure cell symmetries have not been broken
  3. Density functional perturbation theory (DFPT) calculation of phonon modes
  4. Extracting modes with Phonopy
  5. Computing phonon density of states, dispersion, etc.

It is useful to set up different directories corresponding to steps 1 and 3.

$ ls
1-relax/  2-dfpt

The initial structures for MoS\(_2\) come from the Materials Project (mp-2815).

1. Cell & atom relaxation

Files for this section: github link

In order to get accurate phonon modes, it is necessary to first relax the atomic positions and/or lattice constants. VASP provides several different methods for relaxation, provided by specifying the ISIF tag (see here for details).

Generally, there are two different cases:

  1. The desired symmetry of the cell is known, but the atomic positions and/or lattice constants are not known. In this case, you want to enforce symmetry of the starting structure in the POSCAR file. You should use: IBRION = 2, ISYM = 2. The choice of ISIF also needs to be specified. To relax atom positions only (lattice constants fixed), choose ISIF = 2. For relaxation of the lattice constants, choose either ISIF = 3 (cell volume can vary) or ISIF = 4 (cell volume remains fixed).
  2. The symmetry of the initial structure is not known to be correct. In this case, use IBRION = 2, ISYM = 0 (i.e., turn off symmetry). Usually you want ISIF = 3 for this case.

After this calculation, you will want to look at the CONTCAR file that is output. Depending on the choice of parameters in the INCAR file, you may notice that the symmetry of the cell has changed. For example, see the result of the second option above here. This file will need to be modified further (see part 2 below) before use in DFPT calculations.

2. Enforcing symmetries

Files for this section: github link

After performing the relaxation, it is possible that the resulting atomic positions and lattice constants in CONTCAR will not be symmetrized. For example, if using IBRION = 2, ISYM = 0, ISIF = 3, you will almost certainly not have the exact same lattice constants as you started with.

For phonon (DFPT) calculations, the lack of symmetry can eventually lead to issues in understanding the phonon modes. For example, the structure in CONTCAR could be very close to a hexagonal or tetragonal unit cell, but there could be just enough difference in the lattice constants for the cell to be classified as triclinic. This will result in problems later on (e.g., in the assignment of irreducible representations of the normal modes).

To ‘fix’ this problem, you may want to edit the CONTCAR file and enforce the symmetry you desire. For example, you could see values like -0.00001248932473 in the x,y, or z components of the lattice constants. This should most likely be 0, so you can modify and round to 0.00000000000000. After doing this for the lattice constants and atomic positions, it isn’t a terrible idea to run another relaxation, but this time with fixed lattice constants (ISIF =2) and possibly enforcing symmetry this time (ISYM = 2). This will leave you with a structure that has the symmetry properties that you most likely want for phonon calculations.

3. Density functional perturbation theory (DFPT) calculation

Files for this section: github link

After relaxing the cell, you can use the final CONTCAR as input to a phonon calculation (i.e., mv 1-relax/CONTCAR 2-dfpt/POSCAR). Phonon modes can be computed via two different ways: density functional perturbation theory (DFPT) and finite displacements. DFPT requires only one simulation to get the dynamical matrix and compute all modes, while the finite displacements method involves one or more simulations, each displacing a single atom to compute the forces. DFPT offers an all-in-one approach, but it also takes longer to run because all displacements are done in a single simulation. If using a large cell with limited wall time on a cluster, it is possible that the job will not finish.

To perform a DFPT calculation with VASP, choose IBRION = 7 or IBRION = 8 in the INCAR file (an example of an INCAR for DFPT is shown below). IBRION = 8 applies symmetry operations to reduce the number of displacements needed, while IBRION = 7 does not. The IBRION=7 option will perform \(3N_\mathrm{atoms}\) displacements, whereas IBRION=8 option will greatly reduce the number of displacements based on the crystal symmetry. However, IBRION=8 does not allow for the use of NCORE/NPAR parallelization levels, and for larger cells the benefit of being able to use NCORE/NPAR quickly outweighs the benefit of having a fewer number of displacements with IBRION=8. Both IBRION=7 and IBRION=8 allow for KPAR parallelization. However, the memory usage by VASP with k point parallelization is not particularly good, so for large cells KPAR usually needs to be set to a small number to avoid seg faults (typically KPAR ~<= 12). This also contributes to the benefit of IBRION=7 when running on more than a couple of nodes. Finally, for monolayer materials IBRION=8 may incorrectly apply symmetries of the cell including vaccum space to determine the displacement directions, whereas IBRION=7 will not have this issue. Therefore for monolayers, either finite displacements or IBRION=7 should be used.

A typical INCAR file for IBRION=7 is the following:

SYSTEM   = MoS2
NCORE    = 8
KPAR     = 4

ENCUT    = 600
ALGO     = Normal
PREC     = Accurate
EDIFF    = 1.0e-8

IBRION   = 7
NSW      = 1

ISMEAR   = 0
SIGMA    = 0.05

LASPH    = True
LREAL    = False
ADDGRID  = True

NWRITE   = 3
LEPSILON = True

The NWRITE = 3 option is the highest verbosity output option in the OUTCAR file. It can be necessary to use this tag for post-processing of the normal modes, since only the NWRITE = 3 option will print the eigenvectors of the dynamical matrix divided by the square root of the atomic masses. All other values of NWRITE will only write the eigenvectors (without division by square root of mass). This can cause issues with codes that rely on finding the scaled eigenvectors in the OUTCAR file.

The LEPSILON = .TRUE. tag will tell VASP to compute the dielectric matrix, piezoelectric tensor, and Born effective charge tensor using DFPT. (Note you can also compute these using LCALCEPS, but that method does not use DFPT, which is what we are using in this case.) The Born effective charge tensors are necessary for computing infrared (IR) intensity for IR-active vibrational modes.

4. Extracting mode symmetries with Phonopy

Files for this section: github link

After performing the DFPT calculation, it is possible to get mode symmetries from the vasprun.xml file generated by VASP using Phonopy. The first step in Phonopy is to generate a FORCE_CONSTANTS file, done by the following command:

$ phonopy --fc vasprun.xml

Next, we can get the irreducible representations of the modes by creating a file, here named symm.conf

IRREPS = 0 0 0 1e-3
SHOW_IRREPS = .TRUE.

The first line indicates that the irreducible representations of the vibrational modes should be computed at the Gamma point \(\mathbf{k} = (0, 0, 0)\) and the tolerance is set to \(10^{-3}\). The second line tells Phonopy to print the irreducible representations. Other options are available at the Phonopy website.

For our example, after creating symm.conf, issue the following command:

$ phonopy --readfc --dim="1 1 1" symm.conf"

Note the first argument tells Phonopy to read the FORCE_CONSTANTS file, rather than the default FORCE_SETS file generated from the finite displacements method. The second argument specifies the dimensions of a supercell in terms of the primitive cell. Here, we did not create a supercell, so the scaling is 1 in each of the lattice vectors. Note that the use of a primitive cell is only for tutorial purposes (so that the simulations run quickly). In practice, convergence with respect to cell size needs to be tested. Also note that other DFPT implementations do allow for the use of a primitive cell, where phonon frequencies are calculated at other q-points in the BZ. However, this is not implemented in VASP 5. Read more about DIM here.

Phonopy will output information about the space group, point group, and different symmetry operations that leave the cell unchanged.

Unfortunately, C\(_6\) symmetry is currently not supported by Phonopy, so the irreducible representations for 2H phase MoS\(_2\) is not supported.

I will try to submit a fix to this and hopefully it will be available in later Phonopy versions.

5. Phonon dispersion

Another valuable thing to do is plot the phonon dispersion. To do this, we need to choose an appropriate high symmetry path through the Brillouin zone and create a file called band.conf which specifies this path and is read by Phonopy.

The easiest way to find the appropriate high symmetry path is by using the AFLOW website. Go to http://aflow.org/aflow_online.html. This website allows you to copy and paste a POSCAR file from VASP and will automatically figure out the appropriate \(\mathbf{k}\)-space path. Paste the POSCAR file to the input window and select ‘Kpath in the reciprocal space for band structure calculations’, then hit the Submit button on the top right of the window. This will generate a file for use in electron band structure calculations. The \(\mathbf{k}\)-path for the hexagonal lattice we are using is shown at right.

The output from AFLOW can now be used to generate band.conf. Our path is \(\Gamma\)-\(M\)-\(K\)-\(\Gamma\)-\(A\)-\(L\)-\(H\)-\(A\)-\(L\)-\(M\)-\(K\)-\(H\). The band.conf file is:

ATOM_NAME = Mo S
DIM = 1 1 1
BAND =    0.000   0.000   0.000     0.500   0.000   0.000    0.3333  0.3333  0.000   0.000   0.000   0.000     0.000   0.000   0.500     0.500   0.000   0.500     0.3333  0.3333  0.500      0.000   0.000   0.500      0.500   0.000   0.500      0.500   0.000   0.000      0.3333  0.3333  0.000      0.3333  0.3333  0.500   
BAND_LABELS= $\Gamma$ M K $\Gamma$ A L H A L M K H

Once you have created this file, run the following to get a plot of the band structure:

$ phonopy --readfc --dim="1 1 1" -p band.conf

The bands are shown below.

AFLOW citation: S. Curtarolo, W. Setyawan, G. L. W. Hart, M. Jahnatek, R. V. Chepulskii, R. H. Taylor, S. Wang, J. Xue, K. Yang, O. Levy, M. Mehl, H. T. Stokes, D. O. Demchenko, and D. Morgan, AFLOW: an automatic framework for high-throughput materials discovery, Comp. Mat. Sci. 58, 218-226 (2012). [doi=10.1016/j.commatsci.2012.02.005]

6. Phonon density of states

Once FORCE_CONSTANTS has been generated, it is easy to get the phonon density of states:

$ phonopy --readfc --dim="1 1 1" --mesh="64 64 32" -p

This will produce the following plot:

7. Free energy via Phonopy

To get a plot of values of thermal data and save values in “thermal.dat”, do the following:

$ phonopy --dim="1 1 1" --readfc -t -p --mesh="64 64 1" > thermal.dat

This will generate the following plot: