B.K.
Birla College (Autonomous)
Kalyan.
Name: Sonali Ashokkumar Sahu
Roll No. : 22
M.sc (Chemistry)
Topic :
Application of schrödinger
equation to two electron system,
limitation of the equation, need
for the approximate solutions,
method of obtaining the
approximate solution System.
Application of schrödinger equation to two electron system
The Schrodinger equation is used to find allowed energy
levels of quantum mechanical sysyem. The associated wave
function gives the probability of finding the particle at a
certain position.
There is time dependent equation used for describing
progressive wave, And the time independent form of this
equation used for describing standing wave.
Helium atom having 2 electron
rotating around nucleus.
r1 = Distance between nucleus and
electron one.
r2 = Distance between nucleus and
electron two.
r1r2 = Distance between electron one
and electron two
There are 3 types of cordinates.
r1 = coordinate of electron one == 》
r2 = Coordinate of electron two == 》
r12 = Coordinate of nucleus === 》
{ Vector sign for some specific value
and direction. }
Schrodinger equation is,
………………………………………………………………………………………………………….....
For Helium atom the schrodinger equation is,
■ Kinetic engergy (T) ;
The Dependency of wave function for
the helium atom on coordinate of
electron one(e1) and the electron two
(e2).
■ Potential Energy (V)
Equation 3 represent Total Potential Energy for Helium Atom.
Thelast term of the potential energy i.e. V12 is arise a
problem due to it depend upon sets of cordinates
simultaneously repulsion in between two electron.
Hence, Separation of variable cannot use in case of helium
atom.
And we cannot get the exact solution.
Due to this reason, we need to take the help of approximate
solution or approximate method.
LIMITATION OF THE EQUATION:-
1. Schrodinger equation is applicable for the non-
relativistic quantum mechanics.
2. It gives in accurate result.
3. It cannot explain process where particle number is not
preserved.
4. It cannot explain process of particle creation and
destruction.
5. schodinger equation treat all praticle as spin zero
NEED FOR THE APPROXIMATE SOLUTIONS:
The schrodinger equation is a linear parties
differential equation that govern the wave function
of quantum mechanical system.
Approximation methods can be used when Exact
solution to the schrodinger equation cannot be found.
It has therfore proven essential to develop and
efficiently implement mathematical method which
can provide approximation solution.
Method of obtaining the approximate solution of Schrödinger wave equation:-
There are two type of approximate method :-
1. Perturbation theory
2. Variational method
PERTURBATION THEORY:-
Pertubation means “small distirbance”.
In this method, the perturbation operation is
used to find energy of system when it is
distributed or undergoes adjustment in term of
unperturbed quantum system.
In this thoery, perturbation term H’ should be small
( Ho >>> H' )
VARIATION METHOD.
The variational principle means that to find an
approximate ground-state wave function we can use
the variational method: minimize by changing (varying).
Inthis method, a suitable trial function is choosen and is
assumed to be solution of the schrodinger equation.
VARIATION METHOD.
• Using this function, the expectation value of energy of
the system in question is calculated by postulate 3 of
quantum.
• The principle of variation says that, with any trial
function ψ the expectation value of energy Ē will be greater than
the true value E0 which is the lowest. energy eigen value of the
hamiltonian of the system , i.e.
Ē ≥ E0
The proof for this is based on the following two ideas:
1. Even if the wave function is not an eigen function of
the schrodinger equation, it can be expressed as
linear combination of the complete set of normalized
and orthogonal eigen functions
of the system with eigen values E1,E2,E3,……
respectively;
That is
2. The energy associated with the linear combination
function of the type equation (1) is the
weighted average Ē of energy eigen value. Ē is
calculated by formula ,
Ē ≥ E0, where E0 is the lowest energy eigenstate
(groundstate) of the hamiltonian.
Ē = E0, if and only if ψ is exactly equal to the wave
function of the groundstate of the studied system.
In order to apply to variation method, the following steps have
to Taken:
1. Make a Reasonable guess of a series of trial function (on the
basis of some Physical or chemical consideration); the function
must be well-behaved.
2. Calculate Ē in each case.
3. The value of Ē will always be greater than that of E0. The
trial function corresponding to that value of Ē will be best
function.
Thank You
