7.

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

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 Approximation methods

R, r1, r2 = position of the helium nucleus, and the two electrons,

respectively
M, me = mass of the nucleus and the electron
2 ,21, 22 Laplacian operator with respect to the position of the
nucleus, and the two electrons, respectively
M >> me
 The nucleus is approximated to be fixed relative to the motion of
the electrons.
ħ2 2 2 2𝑒2 1 1
− ∇ +∇  𝑟1, 𝑟2 − +  r1, r2
2me 1 2 4𝜋𝜀o 1𝑟 𝑟 2
𝑒 2
+  = 𝐸 𝑟1, 𝑟2
4𝜋𝜀o 𝑟1 − 𝑟2 r1, r2

𝑒2 is called the inter-electronic repulsion term.

4𝜋𝜀𝑜 𝑟1−𝑟2
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 Approximation methods

 If the inter-electronic term were not there,

 the total Hamiltonian operator would be the sum of the two
Hamiltonian operators of two hydrogen atoms.
 the total energy would be the sum of the energies of the two
individual hydrogen atoms, and
 the wave function would be a product of two hydrogen atomic
orbitals.
 There are two major approaches of approximations, the variation
method and the perturbation method.
7.3. The Variation Method
 Applicable to systems for which the wavefunctions for the systems
can be guessed.
 The method allows to obtain an approximation to the ground sate
energy.
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 Approximation methods

 For an arbitrary system, the ground-state wave function 1 and

energy E1 satisfy the Schrӧdinger equation.

H  1  E1 1

Multiply from the left by 1* and integrate over all space, d, to
obtain


  H  d
*
1 1
E1 
  d
*
1 1

Substitute any other non-normalized function o for 1 and

calculate the corresponding energy


  H  d *

E 
   d
*
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 Approximation methods

The variational principle:

E  E1

The equality holds only if  = o, the exact wave function.

 The variational principle says that we can calculate an upper
bound to Eo by using any trial function we wish.


  H  d  E
*

   d
* 1

 The smaller the value of the variation integral, the better the
approximation to the lowest energy will be.

Example: Devise a trial variation function for the particle in a one-

dimensional box of length a.
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 Approximation methods

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  Hdx   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
 *

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 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

 The approximation is acceptable.

Exercise: Consider a one dimensional harmonic oscillator.
Boundary condition:   0 as x  .
Let:   e  cx 2

where c is a variational parameter.

Determine the approximate energy, E.
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 Approximation methods

7.4. The perturbation Method

 The method is suitable for a system which differs only slightly
from the one whose exact solution is known (unperturbed
system)
 The perturbation may be time independent or time dependent.
 Consider a system with a time – independent Hamiltonian
operator which can be solved using the Schrödinger equation:

H o  n( o )  En( o ) n( o )

Where H 0 stands for unperturbed system
 Consider a system with a Hamiltonian operator for which the
Schrödinger equation cannot be solved for the eignfunction and
for the eignvalue.
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 Approximation methods


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.

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 Approximation methods

The difference between the two Hamiltonians is called perturbation

Hence the Hamiltonian for the perturbed system is:

   o

H ' HH
  o 
H H H'

For the above case, the perturbation for harmonic/anharmonic

system is cx3 + dx4.

 The eignfunctions and the eighvalue of a perturbed system must

be related to that of unperturbed system.
 
o 
Let H  H   H '

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 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 )

En  En(o)   En(1)   2 En(2)   ( k ) En( k )

En( k ) and n( k ) are kth order corrections

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 Approximation methods

Solution
First order energy correction term

E (1)
n   ( o )*
m H ' n( o ) d

 Hence the first order correction to the energy is found by

averaging the perturbation over the unperturbed wavefunction.
Letting  = 1

En  En(o)  En(1)

En  E (o)
n   ( o )*
m H ' n( o ) d

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 Approximation methods

First order wavefunction correction:



 H ' n( o ) d
( o )*

 n   n( o )    m( o )
m

m n Em(0)  En(0)

 The wavefunction is summed over all the unperturbed states

Exercise: Apply the perturbation and variation methods for the

ground state of a helium atom.
Solution:

   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

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 Approximation methods

Consider the interelectronic repulsion term, e2 /4or12, to be the

perturbation.
For the first order perturbation,

where j = 1 or 2 (to mean electron 1 and electron 2)

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 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

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 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

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 Approximation methods

Solution

In units of ,

If E(Z) is minimized with respect to Z, Zmin = 27/16.

Back substitution gives:

 It is in good agreement with the experimental result of - 2.9033.

 The value of Z that minimizes E can be interpreted as an effective
nuclear charge.

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