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Ch3 DFT

The document discusses the many-body problem in regular crystals, focusing on the interactions between electrons and the implications of the Pauli Exclusion Principle, exchange interaction, and correlation interaction. It introduces Density Functional Theory (DFT) as a method for investigating the electronic structure of many-body systems, highlighting theorems by Hohenberg and Kohn that underpin the theory. Kohn-Sham DFT is presented as a solution to the many-body problem by treating non-interacting electrons in an effective potential, with methods for approximating exchange-correlation functionals like Local-Density Approximation (LDA) and Generalized Gradient Approximation (GGA).

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Tauhidur Rahman
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8 views4 pages

Ch3 DFT

The document discusses the many-body problem in regular crystals, focusing on the interactions between electrons and the implications of the Pauli Exclusion Principle, exchange interaction, and correlation interaction. It introduces Density Functional Theory (DFT) as a method for investigating the electronic structure of many-body systems, highlighting theorems by Hohenberg and Kohn that underpin the theory. Kohn-Sham DFT is presented as a solution to the many-body problem by treating non-interacting electrons in an effective potential, with methods for approximating exchange-correlation functionals like Local-Density Approximation (LDA) and Generalized Gradient Approximation (GGA).

Uploaded by

Tauhidur Rahman
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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In a many-body problem, the case of a regular crystal, I would like to remind you of some of the

ideas used in this field because the electrons are not only affected by the nuclei in their lattice sites,
but also by the other electrons.
Coulomb potential → just the classical potential that arises from any charged object.
Hartree Potential → the interaction between the electrons in the system is approximated by the
Coulomb potential arising from a system of fixed electrons. Alternatively, each individual electron
moves independently of each other, only feeling the average electrostatic field due to all the other
electrons plus the field due to the atoms but neglecting exchange and correlation effects.
Pauli Exclusion Principle → two identical particles don’t share the same quantum state.
Exchange interaction → this is due to the Pauli Exchange Principle. In this case, if two electrons
have parallel spins then they will not be allowed to sit at the same place at the same time. This
phenomenon gives rise to an effective repulsion between electrons with parallel spins. Not only,
then do we have two electrons interacting via their electronic charge, but also by their spins.
Correlation interaction → this interaction is also a result of the Pauli Exchange interaction. In this
case, there is a correlated motion between electrons of anti-parallel spins which arises because of
their mutual Coulomb repulsion.

Density Functional Theory (DFT)


This is a computational quantum mechanical modeling method used to investigate the electronic
structure (principally the ground state) of many-body systems, in particular atoms, molecules, and
the condensed phases. Using this theory, the properties of a many-electron system can be
determined by using functionals, i.e. functions of another function, which in this case is the spatially
dependent electron density. Hence the name density functional theory comes from the use of
functionals of the electron density.

Density Functional (DF) techniques are based on two theorems, proved by Hohenberg and Kohn in
1964, and on a computational scheme proposed by Kohn and Sham (KS).
 Theorem 1 (Uniqueness): The ground state expectation value of any observable is a unique
functional of the exact ground state electron density  (r ) .
This means that, in the ground state, if the electron density and the functional are known, it is
possible to calculate all properties especially the ground state energy E0 [  0 ] of the system.

 Theorem 2 (Variational principle):  (r ) minimizes the total energy functional E[  ] .


Thus the second theorem establishes a variational criterion for determining  0 (r ) and E0 [  ] . E0 is
found by minimization.

Kohn-Sham DFT
Basically, the kinetic energy has a large contribution to the total energy. Therefore, even the 1%
error in the kinetic energy of the Thomas-Fermi-Weizsacker model prevented DFT from being used
as a quantitative predictive tool. Thus, DFT was largely ignored until 1965 when Kohn and Sham
introduced a method which treated the majority of the kinetic energy exactly. The key idea of that
the intractable many-body problem of interacting electrons in a static external potential is reduced
to a tractable problem of non-interacting electrons moving in an effective potential.

The theory begins by considering the noninteracting reference system: N noninteracting electrons
moving in external potential vs, each in one of N orbitals, ψi. Such a system will be defined by the
Hamiltonian which has an exact eigenfunction that is the single determinant constructed from the N
lowest eigenstates of the one-particle Schrodinger equations

We require that the ground state density be stationary. (In the calculus of variations, the Euler–
Lagrange equation, or Lagrange’s equation, is a 2nd order partial differential equation whose
solutions are the functions for which a given functional is stationary.) The corresponding Euler-
Lagrange equation is
where the Lagrange multiplier is a familiar property to chemists, the chemical potential μ, has been
introduced.
For this system, the kinetic energy and electron density are given by

and

and the total energy is given by

The quantity is well-defined, but not the exact kinetic energy, T[ρ].
Kohn and Sham reformulated the interacting problem so that its kinetic component is defined to be
to give

where J[ρ] is the Coulombic integral expressed in terms of electron density and Exc[ρ] is the
exchange-correlation energy. The Euler–Lagrange equation now becomes

where the Kohn-Sham (KS) effective potential, is defined as

and the exchange-correlation potential, is

Kohn and Sham noticed that equation is the same as that for a non-interacting system moving in the
effective potential . Thus, the exact density can be obtained by solving the N one-particle
Schrodinger equations (the restricted KS equations)

Notice that depends on ρ(r), via equation (6), hence the KS equations must be solved
iteratively.
How to get an approximate XC functional?

1. In Local-density approximation (LDA), the exchange-correlation energy functional Exc[ρ] in


Eq. (1) depends only on the density at the coordinate where the functional is evaluated.

2. LDA treats all systems as homogeneous. However, real systems are inhomogeneous.
Generalized gradient approximation (GGA) takes this into account by including the gradient
of the density into the exchange-correlation functionals.

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