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PPT7
PPT7
Techniques of Approximations
7.1 Introduction
The Schrödinger equation cannot be solved exactly for systems
with inter-electronic repulsion term.
For such systems we must resort to some approximation
methods.
7.2 The He Atom
The Schrödinger equation is:
ħ2 2 ħ2 ħ2
𝛻 − 𝛻12 − 𝛻22 𝑅, 𝑟1, 𝑟2
2𝑀 2𝑚e 2𝑚e
2𝑒2 2𝑒2 𝑒2
+ − − + R, r1, r2
4𝜋𝜀o 𝑅 − 𝑟1 4𝜋𝜀o 𝑅 − 𝑟2 4𝜋𝜀o 𝑟1 − 𝑟2
= 𝐸 𝑅, 𝑟1, 𝑟2
1
Approximation methods
Multiply from the left by 1* and integrate over all space, d, to
obtain
H d
*
1 1
E1
d
*
1 1
H d *
E
d
*
4
Approximation methods
E E1
H d E
*
d
* 1
The smaller the value of the variation integral, the better the
approximation to the lowest energy will be.
Solution:
Let = x(a – x) be the variation wavefunction.
Boundary condition: = 0 at x 0 and x a. Inside the box 0.
2 2
H d 2
2m dx
a a
2 2 d
2
2a3
0 Hdx 2m 0 ax x dx 2 ax x dx 6m
* 2
a a
a5
0 dx 0 x a x dx 30
* 2 2
a
H dx
*
2 a 3 30 5 2
0
a
6m a 5 a 2 m
dx
*
6
Approximation methods
5 2
2
Eo
a m
5h 2 h2
Therefore, 2 2
4 a m 8ma 2
5 1
% error 2 8 100 1.3%
4 8
H n En n
Example:
For a harmonic oscillator
2 2
d 1 2
Ho 2
kx
2m dx 2
For anharmonic oscillator
2 d 2 1 2
H kx cx 3
dx 4
2m dx 2 2
Where H stands for the perturbed system.
If c and d are small, the wavefunction and the eignvalue of the
two Hamiltonian are very similar.
9
Approximation methods
H ' HH
o
H H H'
10
Approximation methods
Let
n( o ) = wavefunction for the unperturbed level
n = wavefunction for the perturbed level
En( o )
= energy level of the unperturbed system
En = energy level of the perturbed system
o
H n H H ' n En n
n n(o) n(1) 2 n(2) ... k n( k )
11
Approximation methods
Solution
First order energy correction term
E (1)
n ( o )*
m H ' n( o ) d
En En(o) En(1)
En E (o)
n ( o )*
m H ' n( o ) d
12
Approximation methods
H ' n( o ) d
( o )*
n n( o ) m( o )
m
m n Em(0) En(0)
h2 ze 2 h2 ze 2
H H 1 H 2 2 1
2
2 2
2
8 m 4 o r1 8 m 4 o r2
13
Approximation methods
14
Approximation methods
Integration result
In units of ,
Letting Z = 2, E = -2.75
The experimental result is - 2.9033.
first-order correction gives a result that is about 5% in error
15
Approximation methods
Variation method
Let the trial function be
where j = 1 or 2.
Let the normalized trial function be o
Use Z as a variational constant
where
16
Approximation methods
Solution
In units of ,
17