Академический Документы
Профессиональный Документы
Культура Документы
II
Thus, in a molecule, the external potential is the attraction to the nuclei
given by the usual expression.
HohenbergKohn existence theorem
(I theorem)
To establish a dependence of the energy on the density, (in the
HohenbergKohn theorem the ground-state density is employed) it is
sufficient to show that this density determines the Hamiltonian operator.
HohenbergKohn existence theorem
(I theorem)
Integration of the density gives the number of electrons, so all that remains
to define the operator is determination of the external potential (i.e., the
charges and positions of the nuclei).
The proof that the ground-state density determines the external potential
proceeds via reductio ad absurdum, that is, we show that an assumption to
the contrary generates an impossible result.
The first HohenbergKohn theorem
The electron density r(r ) determines the external
potential
In short
Thus, let us assume that two different external potentials can each be
consistent with the same non degenerate ground-state density 0.
We are left with an impossible result (that the sum of the two energies
is less than itself), which must indicate that our initial assumption was
incorrect.
Note moreover that the Hamiltonian determines not just the ground-state
wave function, but all excited-state wave functions as well, so there is a
tremendous amount of information coded in the density.
It should therefore be possible to write the electronic energy entirely as a
functional of the density:
Hohenberg and Kohn showed that a universal functional (does not depend on
external potential) FHK[n] exists
In this form it is not practically useful, but it does provide the first step
for deriving the computational techniques on which DFT is based
Only the ground state density n(1) of Hel(1) minimizes the value of its
ground state energy functional (this is the second H-K theorem)
HohenbergKohn II theorem
DFT calculations with the Hohenberg-Kohn approach
Based on the variational principle for the density we can then calculate
the electronic energy by searching for the density that minimizes Eel[n]
The challenge is then shifted from finding the universal H-K functional to finding the
fictitious system of non-interacting electrons which has the same density as the real
one with the interacting electrons
This allows to set up more accurate DFT calculations, as expression for the kinetic energy
of non-interacting electrons is known (no need for approximate kinetic energy functionals
of the density)
In order to see how it works we first need to examine the Schrdinger equation for non-
interacting electrons.
Interacting electrons
Real system
(difficult to simulate, with
interacting electrons)
Orbital-free Kohn-Sham
The LDA approximation assumes that the density is slowly varying and the
inhomogeneous density of a solid or molecule can be calculated using the
homogeneous electron gas functional.
While many ground state properties (lattice constants, bulk moduli, etc.) are
well described in the LDA, the dielectric constant is overestimated by 10-40% in
LDA compared to experiment.
The method can be improved by including the gradient of the density into the
functional.
The generalized gradient approximation GGA is an example of
this type of approach.
Tesi di dottorato: Davide Presti
Local density approximation (LDA)
BLYP
(an example of GGA functional)
B3LYP
(an example of Hybrid/Hyper-GGA functional)
DFT vs post-HF
DFT-Hybrids Post-HF (MP2)
Accuracy
DFT-GGA
DFT-LDA
Hartree-Fock
Computational burden