1

MSE 674 Project I, "Pseudo-Potential" Due: Sept. 4.

Objective:

Electronic wavefunctions are calculated for a one-dimensional system with a square well
potential, leading to the concept of phase-shift, pseudo-potential and a resonant state. We
assume an electron comes from the left (x -) and goes over the potential to the right (x
+). The potential well has the width of w and the depth of V
0
, as below.


Fig. 1 Potential well V(x).
Region I (x < -w/2) V(x) = 0
Region II (-w/2 < x < w/2) -V
0

Region III (w/2 < x) 0


E
-w/2 w/2
-V
0


2
The Hamiltonian is,
H
m
V x = V +

2
2
2
( )
(1)
) 2 / , 2 / ( 0
) 2 / 2 / ( ) (
0
x w w x
w x w V x V
< < =
< < =
(2)

The wave functions in three regions in Fig. 1 are,
Boundary conditions:

1. At x = - w/2,
) 2 ( ' ) 2 ( ' ), 2 ( ) 2 (
2 1 2 1
w w w w + = + + = + (5)
2. At x = w/2,

) 2 ( ' ) 2 ( ' ), 2 ( ) 2 (
3 2 3 2
w w w w + = + + = +
(6)

We now assume

1 1
1 , 1
2 ' 2 '
k k
k k
o
| | | |
= + =
| |
\ . \ .
(7)

2 ' 2
,
w ik ikw
e e = = |
(8)
1
' '
2 2 2
3 3 3
( )
( )
( )
ikx
ik x ik x
ikx ikx
x e
x A e B e
x A e B e
+
+
+

=
= +
= +

( )
( )
( ) x w
w x w
w x
<
< <
<
2
2 2
2
(3)
where
E
k
m
E V
k
m
= + =

2 2
0
2 2
2 2
,
'
(4)

3
and |* is a complex conjugate of |, and |* = |
-1
, * =
-1
. Note that if V
0
= 0, k = k, and = 1,
o = 0, | = . From (5),

* * , *
* , * *
2 2
2 2
o| o|
| |
= =
= =
B B
A A
(9)
From (6),
( )
( )
3 2 2
3 2 2
'
* *
'
*
k
A A B
k
k
B A B
k
| o
| o
=
=
(10)
Combining (9) and (10), we obtain

( )
( )
2
2 2 2
3
3
'
*
i
k
A
k
A e
u
o =
=
(11)
Thus the wave in Region III propagating to the right is
( ) u +
+
= +
kx i
e A
3 3 (12)
The quantity is called the phase shift of the potential.

In this project we assume, w = 1.0 . Then, k
w
=t/w = 3.14
-1
. Thus

2 2
0
37.593
2
w
k
E eV
m
= =
. (13)
This sets the energy scale you should consider.

Task 1: Prove the results above.

4
A. Pseudo-potential by phase-shift

Task 2: Plot as a function of V
0
, from V
0
= 0 up to 1,000 eV, for E = 1 eV. Note that every
time exceeds 2nt, the wavefunction propagating to the right in Region III, +
3+
, is identical to
the one for the principal value of the phase shift, u
p
, where
2
p
n u u t = + . (14)
Thus the potential is effectively shallow. This is the pseudo-potential effect. The potential
which gives
p
is the pseudo-potential of the real potential. Now when u is equal to (2n+1)t, the
pseudo-wave has the opposite sign, but the same shape. So we can define the pseudo-potential
for this case as well. Note that every time u goes through multiples of t, a bound state is created
in the well. So the number of bound state is equal to

p
b
m
u u
t

= . (15)
This point is important to the next discussion about the orthogonality of the real wavefunction to
the bound (core) states.

Task 3: Plot the depth of the pseudo-potential as a function of V
0
.

B. Pseudo-potential by orthogonalization to the core state
Another way of seeing this effect is to see that the wavefunction of the traveling wave, +,
has to be orthogonal to the localized orbital of the core state, o . Then we can generate the true
wavefunction +, starting with a more slowly changing function, , by
o
+ o o =
(16)
+ is the real wavefunction which satisfies the Schrdinger equation, whereas is the pseudo-
function which is the wavefunction for the potential with the depth V
p
, the pseudo-potential. So
in Region II,

5

" "
2 2 2
( )
ik x ik x
x C e D e

= +
(17)

and

2 2
"
2
p
k
E V
m
+ =
(18)

Let us choose V
0
= 200 eV, and calculate the optimum choice of V
p
. In this case we have one
local state at E
L1
= V
0
+ E
0
= - 162.4 eV, with the wavefunction is approximately given by

( )
1, 1,
1,
( ) ( ) 0
( ) 2 cos
I III
II w
x x
x k x
o o
o
= =
=
(19)


and also the second one at E
L2
= -49.6 eV, with the wavefunction is approximately given by

( )
2, 2,
2,
( ) ( ) 0
( ) 2 sin 2
I III
II w
x x
x k x
o o
o
= =
=
(20)


To be exact there are a little bit of tunneling phenomena into Regions I and III, but their
amplitudes are very small, and we neglect them here. Thus

( ) ( ) ( )
( )
2
1 2 2
2
2 2
2 cos " cos
" "
sin sin
2 2 2 2
2
" "
w
w
w
w w
C D k x k x dx
k w k w
C D
k k k k
o
t t

= +
(
| | | |
+
| |
(
\ . \ .
( = + +
+
(
(

}
(21)

6

( ) ( ) ( )
( )
2
2 2 2
2
2 2
2 sin " sin 2
" "
sin sin
2 2
2
" 2 " 2
w
w
w
w w
C D k x k x dx
k w k w
C D
k k k k
o
t t

= +
(
| | | |
+
| |
(
\ . \ .
( = +
+
(
(

}
(22)
Now for Region II

( ) ( )
0 0 p
H H H
V V V V
o
o
o
+ o o
o o
| |
=
|
\ .
= +

(23)

( ) ( ) ( )
0 0 p
H E E V V E V V
o
o
+ o o = + + +
(24),
which should ideally be equal to zero. So we should minimize

( ) ( )
( ) ( )
( )
( ) ( )
2
1
2
1
2 2
* *
0
2 2
2 2
0 0
2
0
2
2
*
0 0
2
[
]
w w
p
w w
p
w
p p
w
I H E dx E V V dx
E V V E V V
E V V
E V V dx E V V
o
o
o o
o
o
o o
+ +
o o
o
o

=

=
= = +
+ + + +
+
= + + +
} }

}
(23)
Task 4: Calculate I as a function of V
p
, and choose the value of V
p
which minimizes I. I is
strictly zero only for V
0
= V
p
, but I becomes a local minimum at the right value of V
p
. Compare
this pseudo-potential to the one chosen earlier by the phase-shift.