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Pseudo Potential

The document discusses the quantum problem related to electron interactions, focusing on the use of pseudopotentials to simplify calculations in Density Functional Theory (DFT). It explains the distinction between core and valence electrons, the computational challenges of including core electrons, and how pseudopotentials allow for efficient calculations by replacing core electrons with an effective potential. Additionally, it outlines the method for constructing norm-conserving pseudopotentials that match wavefunctions and maintain charge density norms.

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8 views7 pages

Pseudo Potential

The document discusses the quantum problem related to electron interactions, focusing on the use of pseudopotentials to simplify calculations in Density Functional Theory (DFT). It explains the distinction between core and valence electrons, the computational challenges of including core electrons, and how pseudopotentials allow for efficient calculations by replacing core electrons with an effective potential. Additionally, it outlines the method for constructing norm-conserving pseudopotentials that match wavefunctions and maintain charge density norms.

Uploaded by

kh.dahan2
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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The Quantum Problem

[ ( ) ( ) ( )] ( ) ( )

where m is the electron mass


En, The eigenvalues correspond to energy levels
and the eigenfunctions or wave functions are given by Ψn;.
Vext The external potential,

The potential arising from the electron–electron interactions can be divided


into two parts
1. classical” electrostatic terms and is called the “Hartree” or “Coulomb”
potential:
( ) ( )
where ρ is the electron charge density
( ) | ( )|

2. Quantum mechanical the “exchangecorrelation” part of the potential,


Vxc effectively contains the physics of the Pauli exclusion principle
the potential depends only on the charge density at the point of
interest
( ) ( )
SCF (Self-Consistent Field)
SCF is a computational procedure used in Density Functional Theory (DFT)
and Kohn-Sham equations to find the electron density that is consistent with
the potential it generates.
Pseudopotential model of a solid
1. Assume an initial electron density ρ.
2. Solve Poisson’s equation to calculate the Hartree potential VH from the
density.
3. Construct the total potential:

where
ionic (external) potential,
: Hartree potential,
: exchange-correlation potential.
4. Solve the Kohn-Sham equation to get wavefunctions and energy
levels
5. Recalculate electron density using:
( ) | ( )|

6. Compare the new density with the previous one,If they’re not equal
(within a set tolerance), repeat the loop until self-consistency is achieved.

Why do we need pseudopotentials?


Pseudopotentials are used to simplify calculations by removing core
electrons, without losing important physical accuracy.When dealing with
heavy atoms like Lead (Pb), there are two types of electrons:
1. Core Electrons:

 Found close to the nucleus (e.g., 1s electrons).


 Highly localized and require very fine numerical resolution.
 Do not participate in chemical bonding.

2. Valence Electrons:

 Located in outer shells (e.g., 6s in Pb).


 Loosely bound and involved in chemical interactions.

The Problem:
 Solving for all electrons (especially core ones) is computationally
expensive.
 Core electrons have complex wavefunctions, which are hard to
represent using simple basis sets like plane waves.

The Solution: Pseudopotentials


Pseudopotentials replace the core electrons and the strong potential
near the nucleus with a smoother, effective potential. This allows us
to:
 Ignore core electrons in calculations.
 Focus only on valence electrons.
 Use simpler and more efficient numerical methods.

Each circle represents an atom in a crystal lattice.Inside each atom:

 The nucleus is at the center.


 Core electrons surround the nucleus but are very close and tightly
bound.
 Valence electrons are further out and are responsible for the chemical
and physical properties of the material.
 Core electrons do not participate in chemical bonding.However,
representing them mathematically is very difficult and
computationally expensive. So instead of calculating the effect of the
nucleus and core electrons every time. we replace them with an
effective potential (pseudopotential) that only affects the valence
electrons.

How is the Pseudopotential Used?


1. We assume that the nucleus + core electrons = one pseudopotential.
2. This pseudopotential is used in the Kohn-Sham equation instead of
the external potential.
3. We only calculate the valence electrons.
4. This greatly reduces the computational cost without losing accuracy
in predicting the material’s properties.
Example:
In silicon (Si)
Electrons in 1s² 2s² 2p⁶ are the core.
Electrons in 3s² 3p² are the valence.
We only use the valence electrons in calculations, and the rest are
replaced by a pseudopotential.

Constructing Pseudopotentials from Density Functional Theory


Define pseudo-wave functions that can be used to define the
corresponding pseudopotential:
The conditions for constructing a pseudopotential,
1. Wavefunction matching outside the core
( )
is a pseudo-wave function for the 3s state
rc defi nes the core size

The pseudo-wavefunction must be identical to the all-electron


wavefunction outside a certain core radius.
2. Norm-Conservation
The integral of the charge density inside the core (norm) must be
the same for the pseudo and the all-electron wavefunctions.
∫ | ( )| ∫ | ( )|

3. Smoothness and nodeless behavior inside the core


Inside , the pseudo-wavefunction must be smooth, continuous, and
free of nodes.
Method of constructing “norm-conserving” pseudopotentials

1. Kerker

( ) ps-wavefunction for angular momentum number

( ) all-electron wavefunction

rc: core radius

r ≤ rc

smooth

nodeless

easily tunable using p(r) is taken to be a polynomial of the form

The parameters, c2n, are fixed by the following criteria:

 The all-electron and pseudo-wave functions have the same


valence eigenvalue.
 The pseudo-wave function is nodeless and be identical to
the all-electron wave function for r > rc.
 The pseudo-wave function must be continuous as well as
the first four derivatives at rc.
| | , | |
 The pseudopotential has zero curvature at the origin. This
construction is easy implement and extend to include other
constraints

Once the pseudo-wave function is constructed, the Kohn– Sham equation


can be inverted to arrive at the ion-core pseudopotential.

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