Dr.

Eman Zakaria Hegazy Quantum Mechanics and Statistical

Thermodynamics Lecture 18

A trial function that depends linearly on the variational

parameters leads to a secular determinant
- as another example of the variational method, consider a
particle in one dimensional box. We should expect it to be
symmetric about x = a/2 and to go to zero at the walls.
- one of the simplest functions with this properties is x n ( a-x)n ,
where n is a positive integer , consequently , lets estimate E o by
using :

c1x (a x ) c 2 x 2 (a x ) 2 (1)

Where c1 and c2 are to be the variational parameters. We find

after the energy of particle in one dimensional box exactly
equal to:

h2 h2
E exact 2
0.125000 (2)
8ma ma 2
Now we will use a trial function to calculate Emin to particle in
one dimensional box.
A trial function can be generally written as:
N
C n f n (3)
n 1

Where the Cn are variational parameters and fn are arbitrary

known functions

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 Dr.Eman Zakaria Hegazy Quantum Mechanics and Statistical
Thermodynamics Lecture 18

Consider

c1f 1 c 2 f 2
Then :

H d (c f 1 1 c 2 f 2 )H (c1f 1 c 2f 2 )d

d c c f Hf
c12 f 1Hf d c c f Hf d c 2 f Hf
d
1 1 2 1 2 1 2 2 1 2 2 2

c12 H 11 c1c 2 H 12 c1c 2 H 21 c 22 H 22 (4)

Where

d
H ij f i Hf (5)
j

We will note that :

d f Hf
d
f i Hf j j i (6)

So Hij=Hji
Using this result, equation (4) becomes

d c 2 H 2c c H c 2 H (7)
H 1 11 1 2 12 2 22

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 Dr.Eman Zakaria Hegazy Quantum Mechanics and Statistical
Thermodynamics Lecture 18

Similary we have

2 2 2
d c S
1 11 2c c S
1 2 12 c 2 S 22 (8)

Where

S ij S ji f i f j d (9)

The quantities Hij and Sij are called matrix elements .

By substituting equations 7,8 into equation 10

H 0d

0
E (10)
d

0 0

We find that :

c12 H 11 2c1c 2 H 12 c 22 H 22
E (c1 , c 2 ) 2 (11)
c1 S 11 2c1c 2S 12 c 22S 22
Before differentiating E(c1,c2) in equation 11 with respect to
c1and c2 , it is convenient to write equation 11 in the form:

E (c1 , c 2 )(c12S 11 2c1c 2S 12 c 22S 22 ) c12 H 11 2c1c 2 H 12 c 22H 22 (12)

If we differentiate equation 12 with respect to c1 we find that
E 2
(2c1 S 11 2c 2S 12 )E (c1 S 11 2c1c 2S 12 c 22S 22 ) 2c1 H 11 2c 2 H 12 (13)
c1

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Dr.Eman Zakaria Hegazy Quantum Mechanics and Statistical
Thermodynamics Lecture 18

E
Because we are minimizing E with repect to c 1 , c1 =0 and so
equation 13 becomes

(2c1 S 11 2c 2S 12 )E 2c1 H 11 2c 2 H 12
(14)
c1 (H 11 ES 11 ) c 2 (H 12 ES 12 ) 0
Similarly by differentiating E(c1,c2)with repect to c2 instead of
c1 we find

c1 (H 12 ES 12 ) c 2 (H 22 ES 22 ) 0 (15)

Equations (14) and (15) constitute a pair of linear algebraic

equations for c1 and c2
This equation is not simply solved but if c1 = c2

H 11 ES 11 H 12 ES 12
0 (16)
H 12 ES 12 H 22 ES 22
To illustrate the use of equation 16 let us go back to solving the
problem of a particle in a one dimensional box variationally
using equation (1)

c1x (a x ) c 2 x 2 (a x ) 2
We will set a = 1. In this case ,
f1 = x (1- x) and f2 = x2 (1- x) 2

[4]
Dr.Eman Zakaria Hegazy Quantum Mechanics and Statistical
Thermodynamics Lecture 18

So, we will solve H11 , H12, H22 , S11, S12 and S22 from the equations
(5) , (9)

H ij f i Hf
d
j

S ij S ji f i f j d
1
h2
d
H 11 f 1Hf 1d x (1 x )

2
x (1 x ) dx
0 2m dx
1
h2
x (1 x ) 0 2dx
2m 0
1
h2
2m 0
2 x 2 x 2
)dx

1
h2 2 3 h2
x x
2

2m 0 3 6m
- As the same you can get H12 and H22

h2 h2
H12 = H21= and H22 =
30m 105m
1

1 dx
2
- Also we can get S11 = f
0

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Dr.Eman Zakaria Hegazy Quantum Mechanics and Statistical
Thermodynamics Lecture 18

1 2

x (1 x ) dx
0

- As the ( x 2x x )dx
2 3 4

same 0

we can 1 2 1 1
10 x 3 x 4 x 5
get S12 3 4 5 30
and S22

1 1
S12 = S21 = and S22 =
140 630
- Substituting the matrix elements Hij and Sij into the
secular determinant gives

1 E 1 E
6 30
30 140
0
1 E 1

E

30 140 105 630
where E = E m/ h2 . The corresponding secular equation is
E 2 - 56 E +252=0
whose roots are

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Dr.Eman Zakaria Hegazy Quantum Mechanics and Statistical
Thermodynamics Lecture 18

56 2128
E 51.065and 4.93487
2
We choose the smaller root and obtain

h2 h2
E min 4.93487 0.125002
m m
Compare with Eexact when a =1

h2
E exact 0.125000
m
The excellent agreement here is better than should be expected
normally for such a simple trial function. Note that E min f

E exact , as it must be.

Example
Using Equation f1=x (1-x) and f2= x2(1-x) 2, show explicitly
that H12=H21
Solution: using the Hamiltonian operator of a particle in a box,
we have

dx x (1 x ) h d x 2 (1 x ) 2 dx
1 2
H 12 f 1Hf 2 0 2m dx 2

[7]
Dr.Eman Zakaria Hegazy Quantum Mechanics and Statistical
Thermodynamics Lecture 18

1
h2
dx
2
x (1 x ) 2 12 x 12 x
2m 0

h2 1 h2

2m 15 30m
1
h2
d
H 21 f 2 Hf 1 0
dx x (1 x )
2 2
2m dx 2 x (1 x ) dx

1
h2
x 2
(1 x ) 2
2dx
2m 0

h2 1 h2

2m 15 30m

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