In this example, we'll look at how to use various pseudopotential (PSP) formats in DFTK and discuss briefly the utility and importance of pseudopotentials.
Currently, DFTK supports norm-conserving (NC) PSPs in separable (Kleinman-Bylander) form. Two file formats can currently be read and used: analytical Hartwigsen-Goedecker-Hutter (HGH) PSPs and numeric Unified Pseudopotential Format (UPF) PSPs.
In brief, the pseudopotential approach replaces the all-electron atomic potential with an effective atomic potential. In this pseudopotential, tightly-bound core electrons are completely eliminated ("frozen") and chemically-active valence electron wavefunctions are replaced with smooth pseudo-wavefunctions whose Fourier representations decay quickly. Both these transformations aim at reducing the number of Fourier modes required to accurately represent the wavefunction of the system, greatly increasing computational efficiency.
Different PSP generation codes produce various file formats which contain the same general quantities required for pesudopotential evaluation. HGH PSPs are constructed from a fixed functional form based on Gaussians, and the files simply tablulate various coefficients fitted for a given element. UPF PSPs take a more flexible approach where the functional form used to generate the PSP is arbitrary, and the resulting functions are tabulated on a radial grid in the file. The UPF file format is documented on the Quantum Espresso Website.
In this example, we will compare the convergence of an analytical HGH PSP with a modern numeric norm-conserving PSP in UPF format from PseudoDojo. Then, we will compare the bandstructure at the converged parameters calculated using the two PSPs.
using DFTK using Unitful using Plots using LazyArtifacts
Here, we will use a Perdew-Wang LDA PSP from PseudoDojo, which is available in the JuliaMolSim PseudoLibrary. Directories in PseudoLibrary correspond to artifacts that you can load using
artifact strings which evaluate to a filepath on your local machine where the artifact has been downloaded.
We load the HGH and UPF PSPs using
load_psp, which determines the file format using the file extension. The
artifact string literal resolves to the directory where the file is stored by the Artifacts system. So, if you have your own pseudopotential files, you can just provide the path to them as well.
psp_hgh = load_psp("hgh/lda/si-q4.hgh"); psp_upf = load_psp(artifact"pd_nc_sr_lda_standard_0.4.1_upf/Si.upf");
First, we'll take a look at the energy cutoff convergence of these two pseudopotentials. For both pseudos, a reference energy is calculated with a cutoff of 140 Hartree, and SCF calculations are run at increasing cutoffs until 1 meV / atom convergence is reached.
The converged cutoffs are 26 Ha and 18 Ha for the HGH and UPF pseudos respectively. We see that the HGH pseudopotential is much harder, i.e. it requires a higher energy cutoff, than the UPF PSP. In general, numeric pseudopotentials tend to be softer than analytical pseudos because of the flexibility of sampling arbitrary functions on a grid.
Next, to see that the different pseudopotentials give reasonbly similar results, we'll look at the bandstructures calculated using the HGH and UPF PSPs. Even though the convered cutoffs are higher, we perform these calculations with a cutoff of 12 Ha for both PSPs.
function run_bands(psp) a = 10.26 # Silicon lattice constant in Bohr lattice = a / 2 * [[0 1 1.]; [1 0 1.]; [1 1 0.]] Si = ElementPsp(:Si; psp=psp) atoms = [Si, Si] positions = [ones(3)/8, -ones(3)/8] # These are (as you saw above) completely unconverged parameters model = model_LDA(lattice, atoms, positions; temperature=1e-2) basis = PlaneWaveBasis(model; Ecut=12, kgrid=(4, 4, 4)) scfres = self_consistent_field(basis; tol=1e-4) bandplot = plot_bandstructure(scfres) (; scfres, bandplot) end;
The SCF and bandstructure calculations can then be performed using the two PSPs, where we notice in particular the difference in total energies.
result_hgh = run_bands(psp_hgh) result_hgh.scfres.energies
Energy breakdown (in Ha): Kinetic 3.1590119 AtomicLocal -2.1424772 AtomicNonlocal 1.6043204 Ewald -8.4004648 PspCorrection -0.2948928 Hartree 0.5515677 Xc -2.4000929 Entropy -0.0031622 total -7.926189833646
result_upf = run_bands(psp_upf) result_upf.scfres.energies
Energy breakdown (in Ha): Kinetic 3.0954187 AtomicLocal -2.3650805 AtomicNonlocal 1.3082675 Ewald -8.4004648 PspCorrection 0.3951970 Hartree 0.5521874 Xc -3.1011669 Entropy -0.0032193 total -8.518860826803
But while total energies are not physical and thus allowed to differ, the bands (as an example for a physical quantity) are very similar for both pseudos:
plot(result_hgh.bandplot, result_upf.bandplot, titles=["HGH" "UPF"], size=(800, 400))