Scribd
Upload
248 views5 pages

Eρ r r r r r: r = F ρ r + ρ r V r d

Dft

Uploaded by

Fahd Elmourabit
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
248 views5 pages

Eρ r r r r r: r = F ρ r + ρ r V r d

Dft

Uploaded by

Fahd Elmourabit
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
You are on page 1/ 5

Density Functional Theory

(introduced for many-electron systems)

The Hohenberg-Kohn theorem states that the ground state electron density
minimizes the energy functional:
r r r r 3
E [ ρ ( r )] = F [ ρ ( r )] + ∫ ( ) ion ( )d r
ρ r V r
an universal
functional

P. Hohenberg and W. Kohn, “Inhomogeneous Electron Gas”,


€ Phys. Rev. 136, B864 (1964)
M. Levy, Proc. Natl. Acad. Sci (USA) 76, 6062 (1979)

The original HK proof applies to systems with nondegenerate ground states.


It proceeds by reductio ad absurdum, using the variational principle. A more
general proof was given by Levy.

• Assume that another functional F’ with the ground state ’ gives rise to the
same density 
• Unless F’ -F=const, ’ since they satisfy different Schroedinger
equations.

E'= Ψ' Hˆ ' Ψ' < Ψ Hˆ ' Ψ = E + F' [ ρ ] − F [ ρ ]


E + E'< E + E '
E = Ψ Hˆ Ψ < Ψ' Hˆ Ψ' = E'+F [ ρ ] − F' [ ρ ]

• Thus F is (within a constant) a unique functional of 

 The minimum value of E is the ground state€ electronic energy


 Since F is a unique functional of the charge density, the energy is
uniquely defined by 
 Electron density is the fundamental variable
 Calculations based on DFT are restricted to systems in their ground
state
 proof of the Hohenberg-Kohn theorem is not constructive, hence the
form of the universal functional F is not known
Since the density can unambiguously specify the potential, then contained
within the charge density is the total information about the ground state of the
system. Thus what was a 4N(3N)-variable problem (where N is the number of
electrons, each one having three Cartesian variables and electron spin) is
reduced to the four (three) variables needed to define the charge density at a
point.

The density determined via the variational equation

δ r r
r [ E [ ρ ( r )] − μ ∫ d r ρ (r )] = 0
3

δρ( r )
exchange
correlation
energy
r r 1 r r 3 r
€
F [ ρ ( r )] = Ts [ ρ ( r )] +
2
∫ ρ (r )VH [ρ (r )] d r + E xc [ρ (r )]
kinetic energy Hartree
density potential

 Ts represents that part of kinetic energy which corresponds to a system


of independent particles with density .
 The Hartree potential VH is found self-consistently
 The exchange correlation energy contains the exchange part of the
energy, plus all the contributions due to the correlations, coming from
the fact that the exact wave function is not a Slater determinant. In
particular, correlations coming from the total kinetic energy enter this
term.
 Ts is not known explicitly for many-fermion systems. One can
approximate it with the ETF expression, but the semiclassical functional
cannot describe quantum shell effects!
Density Functional Theory
Kohn-Sham equations

W. Kohn and L.J. Sham, "Self-Consistent Equations Including Exchange


and Correlation Effects,” Phys. Rev. 140, A1133 (1965)

r r 2
ρ( r ) ≡ ∑ n i φ(r )
i

r h2 r r 2 3
T [ ρ ( r )] = ∑
2m i
n i ∫ ∇φi (r ) d r
€
• Takes into account shell effects
• The link between T and  is indirect, via the orbitals 
• The occupations n determine the electronic configuration
€
Orbitals  form a complete set. The occupations n are given by the
Pauli principle (e.g., n=2 or 0). The variation of the functional can be done
through variations of individual s.p. trial functions with a constrtaint on
their norms. It almost looks like HF, but Ψ H ˆ Ψ is replaced by E[].

ˆ r r €r
{T + V r φ r
KS ( )} i ( ) = E i i (r )
φ Kohn-Sham equation

r r r
VKS ( r ) = V H [ρ ( r )] + Vxc [ ρ ( r )] Kohn-Sham potential (local!)

r δ has to be
Vxc [ ρ (r )] = r E xc ( ρ ) evaluated
δρ ( r ) approximately
Local Density Approximation (LDA) for the exchange+correlation
potential:

• One performs many-body calculations for an infinite system with a


constant density 
• The resulting energy per particle is used to extract the xc-part of the
energy, exc(), which is a function of 
• The LDA of a finite system with variable density (r) consists in
assuming the local xc-density to be that of the corresponding infinite
system with density  =(r):
r r 3
E xcLDA [ ρ ] = ∫ ( ) xc [ ( )] d r
ρ r e ρ r

• The formalism can be extended to take spin degrees of freedom, by


introducing spin-up and spin-down densities (‘Local Spin Density’
formalism, LSD or LSDA)
€

In regions where the charge density is slowly varying, the exchange


correlation energy at that point can be considered the same as that
for a locally uniform electron gas of the same charge density.
Interestingly, the LDA even works reasonably well in systems where
the charge density is rapidly varying. In order to move beyond the
LDA, the addition of gradient corrections to incorporate longer range
gradient effects is necessary.

The LDA is often used in nuclear physics (Brueckner et al., Negele). It


states that the G-matrix at any place in a finite nucleus is the same
as that for nuclear matter at the same density, so that locally one can
calculate G-matrix as in nuclear matter calculation.
The exchange+correlation potential
(an example)

⎧
⎪γ (1+ β1 rs + β 2 rs )
−1
for rs ≥ 1
exc = ⎨
⎪
⎩B + ( A + Crs ) ln rs + Drs for rs < 1
⎛4πρ ⎞1/ 3
rs = ⎜ ⎟ Wigner-Seitz radius
⎝ 3 ⎠
€
The parameters in the above expression depend on the spin polarization;
they are obtained by means of extrapolation between calculated values
€for fully-polarized and non-polarized cases. Calculations were carried out
using the quantum Monte Carlo method. (See, e.g., J. P. Perdew and A.
Zunger, Phys. Rev. B 23 , 5048 (1981).)

∂2E
B = −V
∂V 2 V
0

QuickTime™ and aTIFF (Uncompressed) decompressorare needed to see this picture.

The calculated bulk moduli (from


The calculated minimum energy http://www.physics.ohio-
conformation of acetylcholine showing state.edu/~aulbur/dft/bdft5.html)
electron density isosurface (from

http://www.tcm.phy.cam.ac.uk/~mds21/report/node30.html)

You might also like