The Morse Potential in Quantum Chemistry

Johar M. Ashfaque
The Morse potential realistically leads to dissociation, making it more useful than the usual harmonic
potential. The Morse potential is the simplest representative of the potential between two nuclei in which
dissociation is possible.
The form of the Morse potential in terms of the internuclear distance is


2
r r0
D 1 exp
r0
where r0 is the equilibrium internuclear distance. It is common to define
x=

r r0
r0

so that the potential reads


2
D 1 ex .
The one-dimensional Schr
odinger equation then takes the form


2
~2 d2
x
+
D
1

e
= E
2m dx2

Note. The Taylor expansion of the potential energy operator yields a quadratic leading term.
Define y = x so that
d
dy d
d
=
=
dx
dx dy
dy
which transforms the Schr
odinger equation into

2
~2 2 d2
y

+D 1e
= E
2m dy 2
which becomes
d2 2mD
2 2
dy 2
~


2 !
E
y
1e
= 0.
D

Defining

and
=
obtain

2mD
~
E
D


2 !
d2
2
y
 1e
= 0.
dy 2

Next, change variables to make the equation even more tractable. Define = ey which gives
d = ey dy
and

d
d
= .
dy
d
1

The transformed Schr

odinger equation reads


d

2 !
d d


=0
d

and expanding the square yields



d
d d

2 ( 1) + 2 2 = 0.

For
a = 2 ( 1),

b = 2

the equation becomes

2

d
d2
+
(a + b 2 ) = 0.
2
d
d

One sees immediately that there is going to be a problem here. The ordinary quantum chemistry problems
contain terms arranged in such a way as to guarantee a two term recurrence but th three term recurrence
relations that have been obtained lead to a continued fraction solution in a natural way.