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4 - Density Functional Theory 1

Density functional theory (DFT) describes a system using its electron density rather than its many-body wavefunction. DFT is popular due to its ability to account for electron correlation while being less computationally demanding than other methods. The Hohenberg-Kohn theorems established that the electron density uniquely determines the external potential and energy of the system, allowing the energy to be expressed as a functional of the density. However, an exact form for this universal density functional is unknown.

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223 views24 pages

4 - Density Functional Theory 1

Density functional theory (DFT) describes a system using its electron density rather than its many-body wavefunction. DFT is popular due to its ability to account for electron correlation while being less computationally demanding than other methods. The Hohenberg-Kohn theorems established that the electron density uniquely determines the external potential and energy of the system, allowing the energy to be expressed as a functional of the density. However, an exact form for this universal density functional is unknown.

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AndreaAbdelLatif
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© © All Rights Reserved
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Density Functional Theory

Classification of methods
DFT

An alternative to the HF methods that is also popular


among quantum chemists is density functional theory
(DFT).
The main idea of DFT is to describe the system via its
density and not via its many-body wave function..
DFT is presently the most successful (and also the most
promising) approach to compute the electronic
structure of matter.
DFT

Hohenberg-Kohn and Kohn-Sham


The Nobel Prize 1998

Walter Kohn

5
DFT
Reasons for the popularity of DFT

Its applicability ranges from atoms, molecules and solids to nuclei and
quantum and classical fluids
It takes into account electron correlation while being less demanding
computationally than, for example, CI and MP2.
It can be used to do calculations on molecules of 100 or more atoms in
significantly less time than these HF methods.
DFT
Reasons for the popularity of DFT

DFT predicts a great variety of molecular properties: molecular structures,


vibrational frequencies, atomization energies, ionization energies, electric
and magnetic properties, reaction paths, etc
For systems involving d-block metals, DFT yields results that very frequently
agree more closely with experiment than HF calculations do.
The original DFT has been generalized to deal with different situations: spin
polarized systems, multicomponent systems, superconductors, relativistic
electrons, time-dependent phenomena and excited states, molecular
dynamics, etc
DFT
Looking for the correlation energy

Perform Hartree-Fock (single determinant) calculation


then correct the HF results adding:
a perturbation expansion, like in the MPn methods
or, add more configurations (=slater determinants)
DFT
Looking for the correlation energy

Wavefunction methods (WFT)


Perform Hartree-Fock (single determinant) calculation
then correct the HF results adding:
a perturbation expansion, like in the MPn methods
or, add more configurations (=slater determinants)

Adopt DFT methods, which are in principle exacts


using just 1 determinant

Density functional methods (DFT)


DFT

What is the density?


The electron density is a fundamental quantity in quantum chemistry

r(r ) dr gives the probability of finding an electron in the volume element dr

Its a function of three variable (x,y,z) and is therefore relatively easy to


visualize.
Please note that while r(r ) is a function of just 3 variables, the
wavefunction (x1,y1,z1,,xn,yn,zn) is a function of 3N variables!
DFT

What is a functional?
A FUNCTION takes a number and returns another number

An OPERATOR takes a function and returns another function:

A FUNCTIONAL takes a function and returns a number:

For this reason we can say that a functional maps a function into a
number!
DFT

What is a density functional?

A DENSITY FUNCTION takes the electron density and returns a number:

Integrated over all space gives the number N of electron in the molecule
DFT

DENSITY FUNCTIONAL focuses on functionals that


return the energy of the system

The electronic energy E is said to be a functional of the electron density and


is denoted E[r], in the sense that for a given function r(r), there is a single
corresponding energy.
DFT
Is the (x1,,xN) really needed ?

What can we learn from the density?

Position of nuclei: cusps of the density


Atomic numbers: slope of the density near
the nuclei
Total N of electron:

Knowledge of the density is all that is


necessary for a complete determination of
all ground state molecular properties.

14
DFT

Is the (x1,,xN) really needed ?


Hohenberg-Kohn and Kohn-Sham (1964)

Basic Ideas Behind Density Functional theory


Significance
Knowledge of the density is all that is necessary
for a complete determination of all ground state The wave function of an N-electron
molecular properties. system includes 3N variables, while the
density, r no matter how large the system is,
If one knows the exact electron density, r(r), then has only three variables x, y, and z. Moving
the cusps of this density would occur at the from E[] to E[r] in computational chemistry
positions of the nuclei. significantly reduces the computational effort
needed to understand electronic properties of
atoms, molecules, and solids.
A knowledge of |r(r)| at the nuclei would give the
nuclear charge. It provides some chemically important
concepts, such as electronegativity (chemical
Electron density is an observable. potential), hardness (softness), Fukui function,
response function, etc..
Orbitals are just a mathematical construction.
15
The energy can be obtained from the density only indirectly

Obtain N of electron, Hamiltonian


atomic numbers, Solve Schrdinger
atomic positions equation

Density Wavefunction

Calculate energy and


Is there a way to go
other experimental
from the density
observables from
directly to the energy Energy wavefunction
without having to solve
the Schrdinger
equation ?
Can we express the energy directly in terms of the density?

The answer is no.


Can we express the energy directly in terms of the density?

The answer is no.

The Hamiltonian operator for the electrons:

kinetic energies of Potential energies of the electrons


the electrons interelectronic attraction of the
repulsions electrons to the nuclei

This operator is linear, thus the electronic energy can also be written as
a sum of several terms:
Where we have broken down the electron-electron repulsion energy into
three terms:

This energy arises from the classical electrostatic repulsion between the charge
clouds of the electrons and is correctly accounted for in the Hartree wavefunction.

This energy arises from making the wavefunction antisymmetric with respect to the
interchange of electronic coordinates, and is correctly accounted for in the Hartree
wavefunction.

This is the error associated with the mean-field approximation which neglects the
instantaneous interactions of the electrons. So far we have not wavefunction which
models this part of the energy
The classical potential energy terms of the total energy can be expressed
exactly in terms of the density:
In Hartree-Fock theory, ET, EK and EC, are all orbital
functionals, eg:

No (known) exact expression for the kinetic energy in


terms of r exists.

The exchange energy is non-classical: we can not expect there


should be an expression for the exchange energy in terms of
the classical density
The external potential
The nuclear attraction energy part of the electronic Hamiltonian operator is
called external potential in DFT

External because due to the BO approximation we are doing a quantum


calculation only on the electrons so the nuclei are external fixed objects
which exert their Coulomb potential to the electron
In the language of
DFT, electrons
interact with one
another and with an
external potential.
The First Hohenberg-Kohn Theorem
The electron density (r) determines the external potential

This theorem establishes the existence of a (universal and


unique) energy functional of the density

The Second Hohenberg-Kohn Theorem


Any approximate density which provides the external
potential v(r), determines its own wavefunction.

The second HK theorem can be used to establish a variational


principle for DFT, although it restricts the theory to ground states
The HK theorems are non-constructive, so we dont know
what the form of the universal functional is

Research in the DFT largely falls down to the development


of approximate functionals that model experimental data

Kinetic energy functionals are particularly problematic as


ET is so large and even a small relative error gives large
absolute errors

Almost all DFT calculations rely on the Kohn-Sham


approximation, which avoids the need for a kinetic energy
Functional

Different DFT methods differ in the way they represent EX


and EC

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