BY
AFNAN BAKHT
BAHROZ RASHID
WAQAS LIAQAT
NOMAN KHAN
SHEHRISH AKBAR
Atomic physics
Molecular physics
APPROACHES:
Out of many approaches to solve the many body problem, we will use Density
Functional Theory
Where is Hamiltonian operator corresponding to the total energy of the system. In this case,
it is equal to the sum of total kinetic energy operator of the electrons, Coulomb interaction
between the electrons
nuclei. Now we apply a well know Born Oppenheimer approximation [01] on this Hamiltonian,
in which nuclei are taken at rest as compared to fast moving electrons, so the external potential
become static. The Hamiltonian becomes:
( )
( (
( )
This is a second order differential equation with 3N independent coordinates and is extremely
difficult to handle. We use alternative methods to solve this problem.
position and charges of all nuclei in the molecule, the operator representing kinetic energy or
the electron electron repulsion are independent of the particular molecule.
In the second step we have to find the eigen functions
eigenvalues
ground state
principle, which holds a very prominent place in all quantumchemical applications. We recall
from standard quantum mechanics that the expectation value of a particular observable
represented by the appropriate operator using any, possibly complex, wave function
 
The variational principle now states that the energy computed via equation (111) as the
expectation value of the Hamilton operator from any guessed
 
is identical to
 
ground state. This sure solves the problem but it doesnt simplify our work.
we arrived at the conclusion that the Hamilton operator of any atomic or molecular system is
uniquely defined by N, the number of electrons,
the charges of the nuclei. We went on by saying that once is known, we can of course only
in principle solve the Schrdinger equation.
From the properties of electron density
I.
II.
III.
has maxima, that are actually even cusps, only at the positions
of the nuclei
the density at the position of the nucleus contains information about the nuclear charge
Z
Thus, the electron density already provides all the ingredients that we identified as being
necessary for setting up the system specific Hamiltonian and it seems at least very plausible
that in fact
classically.
In their model Thomas and Fermi arrive at the following, very simple expression for the kinetic
energy based on the uniform electron, a fictitious model system of constant electron density.
The importance of this equation is not so much how well it is able to really describe the energy
of an atom, but that the energy is given completely in terms of the electron density
. TF
model is a perception for how to map a density on to energy without any additional
information required. In particular, no recourse to the wave function is taken. After getting an
expression in which energy is expressed as a functional of density. To find the ground state, we
again employ variation principle. It is assumed that ground state is connected to the electron
density for which the energy according to which the Thomas Fermi equation is minimized under
the constraint.
For realistic systems, it yields poor quantitative predictions, even failing to reproduce some
general features of the density such as shell structure in atoms and Friedel oscillations in
solids.[05]
. The
density thus determines the uniquely corresponding Hamiltonian, the ground state stationary
wave function
The theorem provides the proof that a physically meaning full wave functional can be
uniquely associated with a certain density is physically justified.
Kinetic energy and energy of electronelectron interaction can be expressed by use of
density. The total energy functional for a system of electrons in external potential
expression
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
has the
[ ]
Where
[ ] is called HKfunctional
[ ]
[ ]
If we know
Theorem 2:
The functional E[n] of total energy satisfies a variational with respect to density
The total energy E[n] reaches its minimum value E0 for correct ground state density.
[ ]
Where
system. Ground state density is sufficient to obtain all properties of the system but how to find
that a certain density is really a ground state density that we are looking for.
In plane words this theorem states that
density of the system, delivers the lowest energy if and only if the input is true ground state
energy of the system. This is nothing but variational principle.
[ ]
[ ]
[ ]
[ ]
Now for any trial density n(r) which satisfy the necessary boundary condition such as
and
. The energy
obtained from above equation represent an upper bound to true ground state energy
result if and only if the exact ground state density is inserted in the above equation. Now the
trial density defines its own Hamiltonian
. This wave
function can now be taken as trial wave function for the Hamiltonian generated from true
external potential
 
.Thus, we arrive at
[ ]
[ ]
[ ]
 
ConstraintsSearch Formulation
HKtheorems imply that for any arbitrary density
which is called Vrepresentable. Due to this fact it is possible to construct such densities which
are not Vrepresentable. This implication obviously leads to formal problems which can
circumvent by more general formulation of HKtheorem called constrainedsearch formulation
[07].
The densities which are Vrepresentable are called Nrepresentable if it can be constructed
from antisymmetric Nparticles wave function. Based on so called Nrepresentable densities, a
more general and modified scheme for
to
[ ]
[ ]
The notation
to density
[ ]
 [ ]
leading
[ ]
 [ ]
Now as Ritz Variational Principle comprises over all allowed wave function within its search
while constrainedsearch is limited to wave functions that generates
. Now the
minimization runs without requiring Vrepresentability over all wave functions. A relation of the
Ritz variational principle in with variational principle of the 2nd HKTheorem can be established
by simply separating the search over all wave functions
variation, into two separate searches that lead to a variation performed using the second HKTheorems.

10


[ ]
The 1st minimum search runs over all wave functions resulting the density
. The second
search after that lifts the constraint to a particular density and extends the new search
over all the densities. Though the HKtheorems and the constrainedsearch
formulation create a strict mathematical framework and now the existence of the total energy
functional is ensured, but one still has no practically feasible scheme to treat the N interacting
electrons at hand at this point which is solved by Kohn and Sham [08].
11
KohnSham Approach
The main idea of the Kohnsham (KS) method is to map the interacting electrons system to a
fictitious system of noninteracting electrons that produce exactly the same ground state
density and ground state energy as the interacting system. In this system, they behave as a
charge fewer particles which do not interact with each other but each of the electrons felt the
field produced by all other electrons of the system. In other words, the KS scheme represents a
meanfield theory.
The wave function
[n] of the KS system is defined as the wave function that minimizes the
[ ]
Where
 
definition is
[ ]  [ ]
[ ]
[ ]
 [
[ ]
 [ ]
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
which contains difference of the kinetic energies plus difference of the expectation values of
the electronelectron interaction of the systems.
[ ]
[ ]
[ ]
12
[ ]
[ ]
Here the problem is in reformulating in a way that main part of the energy is treated in an exact
manner and all other unknown contributions are absorbed in the exchangecorrelation
functional
only transferred onto the problem of finding the exact expression for the function
has
[ ] of
By varying the expression (3.20) with respect to density yields the EulerLagrange equation of
the KS theory
[ ]
[ ]
[ ]
[ ]
[ ]
13
To construct such energy functional there are no simple methods but it is certainly possible to
separate the exchange part from the correlation part. The same holds for the exchange and
correlation potentials as the functional derivative of the energy functional with respect to the
density
[ ]
[
[ ]
[ ]  [ ]
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
So
[ ]
Now put the value of
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]  [ ]
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]
[ ]  [ ]
So by knowing the values of the four terms on the right side of this equation we can easily find
the correlation functional.
14
along with the correction for the selfinteraction and the component of the kinetic energy not
covered by the noninteracting reference system. One has to approximate the exchange corelation functional. One of the oldest and most known approximation (LDA), which is proposed
by Kohn and Sham themselves and it lies at the roots of DFT and KSformalism.
The original physical system for LDA is homogeneous electron gas, means a system of electrons
which moves on a uniform background of positive charge in such a way that the entire system
becomes electrically neutral. The electrons and the volume of gas V approach to infinity, while
the electron density
spatial point . Inhomogeneous system of electrons such as atom, molecule or solid are treated
as homogenous system with the corresponding exchange and correlation energy
per electron at point by the associated homogenous electron gas with density at each point .
Hence, LDA approximation is most suitable for slowly varying density systems. However in solid
state physics LDA is the most employed scheme while in chemistry it has no comparable impact
in which the atoms and molecules are parameterized by a rapidly varying density. As the
homogenous electron gas is determined by its density, energy due to the exchangecorrelation
within LDA approximation is calculated by integrating the parameter
the local density
This energy is again separated between its exchange and correlation term
[ ]
15
weighted with
)
was originally derived by Dirac [10] and given
as
Where
explicit expression for the corelation energy term. Ceperley and Alder used the quantum based
Monte Carlo scheme to calculate the total energy for a homogenous electron gas and attained
the correlation energy by subtracting the corresponding exchange and kinetic energies [11].
Various authors have presented analytical expressions of
interpolation schemes. The most widely used representations of
based on sophisticated
are the ones developed
by Vosko, Wilk, and Nusair (VWN) [12], 1980, while the most recent and probably also most
accurate one has been given by Perdew and Wang [13], 1992. VWN interpolated this data and
formed the LDA correlation
Where
,
,
)]]
at a
particular point , but to supplement the density with information about the gradient of the charged
density
in order to account for the nonhomogeneity of the true electron density which is varying
16
[ ]
This approach is known as generalized gradient approximations (GGA) and generally is given by a
functional which explicitly contains density gradient
[ ]
[ ]
In most of the cases GGA functionals for the exchange part can be written as
[ ]
Where the argument of
is a dimensionless parameter
Where F(s) is a scaling function that can have in practice a pretty complicated form. Here,
stands
GGA functional yields often better results than the LDA. However, some of these functionals may not
necessarily based on the new physical ideas, while some are of the semi empirical character; contains
fitting parameters and sometimes are solely constructed in order to satisfy required boundary
conditions and gain fine results in an adequate computing time. Oftenly, these are optimized in order to
gain good energy value results and do not give bearable results for the related potentials. Some of the
most important and most widespread GGAs are
17
The functional derivative of the general GGA exchange correlation functional is given by [21]
[
)]
)]
From the above expressions it can be seen that GGA potentials contain even higher density
derivatives than the related energy functionals and together with the already some complicated
functionals of energy, the analytical equations for the potentials can become highly complicated
18
Where
Here
energy and
The particular selection of the functions was motivated by Slater who noted that plane waves are
solutions of the Schrdinger equation for constant potential, while radial functions are solutions for a
spherical potential, for
approximation and is very good for closepacked (e.g. fcc and hcp) materials. The double
representation defined by the above equation is not certain to be continuous on sphere boundaries,
as it is supposed for the kinetic energy to be well defined. Thus a constraint on the APW method is
imposed by defining
in terms of the
19
Here the origin is taken at the center of the sphere and R is sphere radius. Thus
determined by the planewave coefficients
20
are completely
as
satisfies
[
In the nonrelativistic case, on sphere boundaries these functions are matched to values and
derivatives of plane waves. Plane waves augmented in this way are called as the LAPW basis
functions. In the form of this basis, the wave functions
[
Where
approximations are not made and consequently such a method is often called as FullPotential
LAPW (FPLAPW). LAPW method is better than the APW. In the former, at a given kpoint accurate
energy bands are obtained with single diagonalization, while for APW method the diagonalization is
required for each band. Moreover, LAPW basis is more flexible inside the spheres because it has two
radial functions instead of one. However, there is a price to be paid for the flexibility. This arises due
to the requirement that the basis functions must have continuous derivatives. Higher value of plane
wave cutoff is needed to achieve a given level of convergence. In the WIEN2K code, the total energy
is calculated according to the Weinert scheme [23]. The cutoff parameter
convergence of the basis set and it is usually takes between 6 to 9. The
controls the
radii and is the smallest of all of the atomic sphere radii in the unit cell and
is magnitude of the
largest K vector. Much higher angular momenta in the wave functions are required (typically
to 12 for accurate calculations) to satisfy the continuity conditions accurately.
21
References
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22
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