electron interacting with nuclie & electron –
MANY BODY
SCHRODINGER
EQUATION
We generally deal with single aton or electron
state because that’s the most easy . In
practical world we have to deal mostly with
bunch of nuclie and bunch of electron , which
makes this sort of a very complicated
equation to solve . So we just try to make
things bit simpler and easier.
ℋ𝜑[{𝑟𝑖 } , {𝑅𝑙 }] = 𝐸𝜑[{𝑟𝑖 } , {𝑅𝑙 }] (1)
This above is many body schrodinger equation
The first thing we apply to make things
simpler is BORN-OPPENHEIMEN
APPROXIMATION , It basically says that the
nuclie , they are big & heavy and are slow
whereas the electrons are small & fast this
means that you can decouple the dynamics of
the nuclie & electron.
We concentrate first on solving the ground
state of the electron for one finite set of
atomic position .
THE SCHRODINGER EQUATION FOR
ELECTRON
𝐻𝜑(𝑟1 , 𝑟2 , 𝑟3 , 𝑟4 . . . 𝑟𝑛 ) = 𝐸𝜑(𝑟1 , 𝑟2 , 𝑟3 , 𝑟4 … 𝑟𝑛 )
The electronic Hamiltonian consist of 3 terms
𝑛 𝑛
ℏ2
̂ =−
ℋ ∑ ∇2𝑖 + ∑ 𝑉𝑒𝑥𝑡 (𝑟𝑖 )
2𝑚𝑒
𝑖 𝑖
+ ∑ 𝑈(𝑟𝑖 , 𝑟𝑗 )
𝑖 =1
𝑗> 1
Now ℋ ̂ only consist of terms which include
electrons , we have the kinetic energy term &
then we have the potential energy term of
electron repulsion .
Lets understand the complexity we would
have faced by using schrodinger equation
with an example
𝑐𝑜2 = 22 𝑒𝑙𝑒𝑐𝑡𝑟𝑜𝑛
Each electron is described by 3 spatial co-
ordinate , which makes our schrodinger
equation a 66-D problem.
Solving the schrodinger equation for a
material with 66-D is practically tricky thing to
do , it will just make our calculations heavy
and nothing more . Hence we started looking
for alternative.
From wave form to electron
density
Define the electron density
𝑛(𝑟) = 𝜑 ∗ (𝑟1 , 𝑟2 . . . . 𝑟𝑛 )𝜑(𝑟1 , 𝑟2 . . . . 𝑟𝑛 )
That reduces from 3N dimension to 3
spatial dimension so the electron density
is only 3-D.
ANOTHER APPROXIMATION
Assume the electron as a point charge in the
field of all other electron that would simplify
the main electron problem to many one
electron problem .
𝜑(𝑟1 , 𝑟2 , 𝑟3 , 𝑟4 . . . 𝑟𝑛 ) = 𝜑(𝑟1 )* 𝜑(𝑟2 )*.. 𝜑(𝑟𝑛 )
We can redefine the electron density in terms
of individual electron wave function.
𝑛(𝑟) = 2 ∑ 𝜑𝑖∗ (𝑟)𝜑𝑖 (𝑟)
𝑖
DFT (HOHENBERG & KOHN)
DFT is based on two theorems
T1: The ground state energy is a unique
functional of the electron density
𝐸 = 𝐸[𝑛(𝑟)]
Functional → function of function
 Electron density is all we need to define the
total ground state energy .
T2: The electron density that minimizes the
energy of the overall functional is the true
ground state electron density
𝐸[𝑛(𝑟)] > 𝐸𝑜 [𝑛𝑜 (𝑟)]
The Energy Functional
𝐸[{𝜑𝑖 }] = 𝐸𝑘𝑛𝑜𝑤𝑛 [{𝜑𝑖 }] + 𝐸𝑥𝑐 [{𝜑𝑖 }]
−ℏ
𝐸𝑘𝑛𝑜𝑤𝑛 [𝜑𝑖 ] = ∑ ∫ 𝜑𝑖∗ ∇2 𝜑𝑖 𝑑3 𝑟
𝑚𝑒
+ ∫ 𝑉 (𝑟)𝑛(𝑟)𝑑3 𝑟
ℰ2
+ ∬ 𝑛(𝑟)𝑛(𝑟 ′ )𝑑3 𝑟𝑑3 𝑟 ′
2
+ 𝐸𝑖𝑜𝑛
PSEUDOPOTENTIALS
In terms of physical quantities like chemical
bonding and other characterstics of the
material which we care about are mainly
characterized by outer electrons or we can
say valance electron . so to make our life a bit
easier for ourselves , lets not consider all the
electron energy rather lets consider on;y the
the outer electron and just freeze the inner
electron that makes the calculation too easy ,
because the inner electron ,are now like big
sum of effective positive potential .
Pseudopotential replaces the electron density
from a chosen set of core electron with a
smoothed density . frozen core approximation
is the main outcome of pseudopotential.

𝐸𝑥𝑐 [{𝜑𝑖 }] → Exchange co-relation functional The pseudopotential method is an

approximate technique to reduce the
➔ Includes all quantum mechanical numerical effort to determine the energies
terms and wave functions , by neglecting cleverly
➔ Not known , need to be approximated the bound states, necessary to account for
the singularity caused by the nuclei. Since the
THE KOHN SHAM SCHEME
pseudopotential technique is an approximate
It helps to solve a set of single electron wave theory ,it ignores a large part of the total
function that only depends on 3-spatial charge density .
variables 𝜑(𝑟)
ℏ 2
[− ∇ + 𝑉(𝑟) + 𝑉𝐻 (𝑟) + 𝑉𝑋𝐶 (𝑟)]𝜑𝑖 (𝑟)
2𝑚
=∈𝑖 (𝑟)𝜑𝑖
There are few steps involved in this process

Step 2
Step 1 Solve kohn sham equation
Trail n(r) with n(r) . obtain single
Electron density electron wave function
𝜑𝑖 (𝑟)

Step 3
Calculate the electron density
based on the single electron
` wavefunction

n(r) = 2 ∑ 𝜑𝑖∗ (𝑟) 𝜑𝑖 (𝑟)

Step 4
Comparision
a) if different, the process begins from step
2 with new n(r).
b) if identical then ground state density is
obtained