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Tutorial Uspp

The document discusses norm-conserving pseudopotentials (NCPP) and ultrasoft pseudopotentials (USPP) used in plane-wave density functional theory calculations. NCPP represent electron-ionic core interactions with a soft potential for valence electrons. They allow accurate calculations with moderate plane-wave basis sets but require large basis sets for hard systems like transition metals. USPP give up norm conservation to further soften the pseudopotential and reduce plane-wave cutoff requirements, but introduce additional terms in calculations due to augmentation charges. The plane-wave cutoff and augmentation charge cutoff must be appropriately set for USPP calculations.

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Vivek Satyanand
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50 views12 pages

Tutorial Uspp

The document discusses norm-conserving pseudopotentials (NCPP) and ultrasoft pseudopotentials (USPP) used in plane-wave density functional theory calculations. NCPP represent electron-ionic core interactions with a soft potential for valence electrons. They allow accurate calculations with moderate plane-wave basis sets but require large basis sets for hard systems like transition metals. USPP give up norm conservation to further soften the pseudopotential and reduce plane-wave cutoff requirements, but introduce additional terms in calculations due to augmentation charges. The plane-wave cutoff and augmentation charge cutoff must be appropriately set for USPP calculations.

Uploaded by

Vivek Satyanand
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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NC and US Pseudopotentials

July 22, 2008


Norm-Conserving Pseudopotentials

Electron-ionic core interactions can be represented by a nonlocal Norm-Conserving


Pseudopotential (NCPP): a soft potential for valence electrons only (core
electrons disappear from the calculation) having pseudo-wavefunctions containing
no “orthonormality wiggles”

3S AE
3P AE
3D AE
3S PS
3P PS
3D PS

0 1 2 3 4 5 6 7 8
r (a.u.)
Norm-Conserving Pseudopotentials

In many systems, NCPP’s allow accurate calculations with moderate-size (Ec ∼


10 − 20Ry) plane-wave basis sets

-15.695
Etot(Si) vs ecutwfc
-15.7

-15.705

-15.71

-15.715

-15.72

-15.725

-15.73

-15.735

-15.74

-15.745
10 15 20 25 30 35 40
Norm-Conserving Pseudopotentials:

Norm-Conserving, DFT-based PPs were introduced by Hamann, Schlüter, Chiang in


1979. For a given reference atomic configuration, they must meet the following
conditions:

• ǫps ae
l = ǫl

• φps
l (r) is nodeless

• φps
l (r) = φ ae
l (r) for r > rc

Z Z
• |φps 2 2
l (r)| r dr = |φae 2 2
l (r)| r dr
r<rc r<rc

where φae
l (r) is the radial part of the atomic valence wavefunction with l angular
momentum, ǫael its orbital energy.
The core radius rc is approximately at the outermost maximum of the wavefunction.
Features of Norm-conserving Pseudopotentials:

+ transferrable: they reproduce the logarithmic derivatives, i.e., the scattering


properties, of the true potential in a wide range of energies.
   Z rc
d d
−2π (rφ(r))2 ln φ(r) = 4π |φ(r)|2r 2dr
dǫ dr rc 0

valid for any regular solution of the Schrödinger equation at energy ǫ.

– non local: there is one potential per angular momentum:


X
ps
V (r) = Vl (r)|lihl|.
l

It is very convenient to recast NCPP’s into a separable, fully nonlocal form:


X
V̂ ≡ Vloc(r) + |βniDnmhβm|
nm

The separable form usually yields good results, but beware of ghosts states
Desirable characteristics of a Pseudopotential:

• Transferability: can be estimated from atomic calculations on different


configurations. In many cases simple unscreening produces an unacceptable loss of
transferability. May require the nonlinear core correction:

Vlps(r) = Vl (r) − VH (nps(r)) − Vxc(nc(r) + nps(r))

where nc(r) is the core charge of the atom (Froyen, Louie, Cohen 1982)

• Softness: atoms with strongly oscillating pseudo-wavefunctions (first-row elements,


elements with 3d and 4f valence electrons) will produce hard PPs requiring
many PWs in calculations. Larger core radius means better softness but worse
transferability. Various recipes to get optimal smoothness without compromising
transferability: Troullier and Martins (1990), Rappe Rabe Kaxiras Joannopoulos
(1990)
Limitations of norm-conserving pseudopotentials

NCPP’s are still “hard”and require a large plane-wave basis sets (Ec > 70Ry) for
first-row elements (in particular N, O, F) and for transition metals, in particular the
3d row: Cr, Mn, Fe, Co, Ni, ...

Even if just one atom is “hard”, a high cutoff is required. This translates into large
CPU and RAM requirements.
Ultrasoft (Vanderbilt) pseudopotentials (USPP) are devised to overcome such a
problem: give up norm consevation keeping transferability.

3d pseudo- and all-electron


orbitals for Cu (Laasonen et al,
Phys. Rev. B 47, 10142 (1993))
X XX
2
n(r) = |ψi(r)| + hψi|βl iQlm(r)hβm|ψii
i i lm
where the Qlm (“augmentation charges”) are:

Qlm(r) = φ∗l (r)φm(r) − φe∗l (r)φem(r)

|βl i are “projectors”


|φli are atomic states (not necessarily bound)
|φeli are pseudo-waves (coinciding with|φli beyond some “core radius”)
In practical USPP, the Qlm(r) are pseudized.
Ultrasoft pseudopotentials
X
V̂U S ≡ Vloc(r) + |βl iDlmhβm|
lm

Orthonormality with USPP:


Z X
hψi|S|ψj i = ψi∗(r)ψj (r)dr + hψi|βl iqlmhβm|ψj i = δij
lm

Z
where qlm = Qlm(r)dr

Generalized eigenvalue problem:

[H − εiS] |ψii = 0
Plane-waves + Ultrasoft pseudopotential calculations

• there are additional terms in the charge density, in the forces ...

• electronic states are orthonormal with an overlap matrix S: hψi|S|ψj i = δij

• the ”augmentation charges” typically require a larger cutoff for the charge density.

Input parameter: ecutrho (SYSTEM namelist)

Default value is ecutrho = 4 × ecutwf c (OK for NC PP)

For US PP a larger value ecutrho ≈ 8 × ecutwf c is often needed.


-87.84
Etot(Cu) vs ecutwfc

-87.845

-87.85

-87.855

-87.86

-87.865
10 20 30 40 50 60 70

Is it variational ?
-87.832
Etot(Cu) vs ecutwfc, ecutrho=4*ecutwfc
Etot(Cu) vs ecutwfc, ecutrho=240
-87.834

-87.836

-87.838

-87.84

-87.842

-87.844

10 20 30 40 50 60 70

With the appropriate ecutrho, an ecutwf c of 25-30 Ry is fine.

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