1.

Schr odingers Equation for the Hydrogen Atom

We solved the Schrodinger equation for the case of a three-dimensional innite
square well and found that for each dimension we introduce a quantum number.
In the case of the innite square well the quantum numbers were independent
of one another - i.e., the value of one did not inuence the value of another.
In addition, we found that the energy states are often degenerate when there is
a degree of symmetry in the system. We now want to look at the case of the
hydrogen atom. Here the potential energy of interaction between the electron
and the proton arising from a radial force depends only upon the distance r from
the proton to the electron, and not on the particular location of the electron (i.e.,
the particular value of or ).
x
y

r
z
Polar Coordinate System used for the Hydrogen Atom
The Schrodinger equation

h
2
2m
_

2
x
2
+

2
y
2
+

2
z
2
_
(r) +
_
k
Ze
2
r
_
(r) = E(r)
can be written in terms of r, , and , by using the relations
x = r sin cos
y = r sin sin
z = r cos
The result, after some algebra, is:
_

h
2
2m
_
1
r
2

r
_
r
2

r
__

h
2
2mr
2
_
1
sin
_

sin

_
+
1
sin
2

2
__
(r)+U(r)(r) = E(r)
Now this equation can be written in the form:
_
_
_

p
2
r
2m


L
2
,
2mr
2
_
_
_
(r) +U(r)(r) = E(r)
where
p
2
r
= h
2
_
1
r
2

r
_
r
2

r
__
is the square of the radial part of the momentum, and

L
2
,
= h
2
_
1
sin
_

sin

_
+
1
sin
2

2
_
is square of the angular momentum L
,
which is only a function of the angles
and .
To solve this equation, we assume that (r) is separable so that it can be
written as the product of a function of the radius only with a function which is
only dependent upon and , i.e., we assume
(r) = R(r)Y (, ).
As shown below, Schrodingers equation in r, , and can then be separated
and written in terms of two equations, one dependent only upon the radius and
containing the electrostatic potential energy term, and the other dependent only
upon the angles and but which is independent of the force. We write

p
2
r
2m
R(r)Y (, )

L
2
,
2mr
2
R(r)Y (, ) +U(r)R(r)Y (, ) = ER(r)Y (, )
which simplies to give
Y (, )
_

p
2
r
2m
R(r)
_

R(r)
2mr
2

L
2
,
Y (, ) +U(r)R(r)Y (, ) = ER(r)Y (, )
2
and, dividing by (r) = R(r)Y (, ), we obtain
1
R(r)
_

p
2
r
2m
R(r)
_

1
2mr
2
1
Y (, )

L
2
,
Y (, ) +U(r) = E.
Multiplying this last equation by 2mr
2
we obtain
r
2
R(r)
_
p
2
r
R(r)
_

1
Y (, )

L
2
,
Y (, ) = 2mr
2
[E U(r)]
which we can separate into terms which are functions only of the radius, and
terms dependent only on the angles:
r
2
R(r)
_
p
2
r
R(r)
_
+ 2mr
2
[E U(r)] =
1
Y (, )

L
2
,
Y (, )
Both sides of this last equation must be equal to some constant for the equation
to be valid for all r, , and . We will express this constant as h
2
. This gives us
two equations,
r
2
_
p
2
r
R(r)
_
+
_
2mr
2
[E U(r)] h
2

_
R(r) = 0
and

L
2
,
Y (, ) = h
2
Y (, )
This last equation is an eigenvalue equation for the angular momentum op-
erator. Since there is no external torque in this system, the angular momentum
of the system must remain constant. This last equation simply states that the
square of the angular momentum operator acting on the eigenfunction of the an-
gles is some constant times that function. The value of the constant will change
as the function Y (, ) changes, but for a given function the angular momentum
is xed! The value of the quantum number , then, is related to the total angular
momentum of the system. When the complete solution of the dierential equation
is determined, we nd that the values of are given by
= ( + 1)
where is an integer. This means that the total angular momentum of the system
is given by
|L| = h
_
( + 1)
3
which is a little dierent from the form of the solution assumed by Bohr. Bohr
assumed that the angular momentum was given by
L = n h
where n was an integer. You will notice, however, that for large values of the
constant , these two expression give approximately the same result.
We now want to look in more detail at the the angular equation, which, when
fully expanded, can be written:

L
2
,
Y (, ) = h
2
_
1
sin
_

sin

_
+
1
sin
2

2
_
Y (, ) = h
2
Y (, )
Just as was done above, this equation can be separated into two terms, each of
which depends upon a dierent angle. Writing the equation
_
sin
_

sin

_
+

2

2
_
Y (, ) = Y (, ) sin
2

we can move all the partials with respect to to one side of the equation and all
the partials with respect to to the other side
_
sin
_

sin

_
+ sin
2

_
Y (, ) =

2

2
Y (, )
We now assume that the function Y (, ) is separable so that Y (, ) = ()(),
giving
_
sin
_

sin

_
+ sin
2

_
()() =

2

2
()()
or
1
()
_
sin
_

sin

_
+ sin
2

_
() =
1
()

2

2
()
Again we see that each side of this equation must be equal to some constant which
we will designate as m
2
giving the two equations
1
()
_
sin
_

sin

_
+ sin
2

_
() = m
2
4
and

1
()

2

2
() = m
2
The second of these two equations is trivial to solve. We obtain a set of
solutions of the form:

m
() = Ae
im
where m must be an integer for the function to be physical (i.e., the value of the
function must repeat for every complete cycle of the angle ). The indicates
that the electron movement is equally likely in either the + direction of the
direction (clockwise or conter-clockwise). But since it cannot move in both at
the same time, then we choose the + sign and allow m to take on values both
positive and negative. The fact that m is restricted on a physical basis, means
that the solutions of the () equation are inuenced by this quantum number
and therefore that the values of which give reasonable results depend upon the
values of m.
One can show that the z component of the angular momentum is given by
L
z
= i h

so that
L
2
z
Y (, ) = h
2

2

2
Y (, )
which leads to the eigenvalue equation
L
2
z
() = h
2
m
2
()
We see, then, that the z component of the angular momentum is quantized and
can take on only certain values. This has some very interesting consequences
which we shall discuss later.
The () equation is not quite so simple. The solution to this equation is the
associated Legendre Polynomials. The normalized solutions for Y (, ) are the
so-called spherical harmonics. The rst few of these are given below:
Y
0,0
=
_
1
4
Y
1,0
=
_
3
4
cos
5
Y
1,1
=
_
3
8
sin e
i
Y
2,0
=
_
5
16
_
3 cos
2
1
_
Y
2,1
=
_
15
8
sin cos e
i
Y
2,2
=
_
15
32
sin
2
e
i2
and a representative set are plotted on the next page. The general formula for
the spherical harmonics is
Y
l,m
(, ) =

_
(2 + 1) ( |m|)!
4 ( +|m|)!
e
im
P
l,m
(cos )
where = (1)
m
for m 0 and = 1 for m 0, and where P
l,m
(cos ) are the
Legendre Polynomials. The values which the quantum number m can take on
must be integers to satisfy the condition that the wave function be periodic in
the angle . For the angular wave functions Y
l,m
(, ) to be normalizable, we nd
that the value of the quantum numbers m and must be related by the equation
m +
Remember that the quantum number is related to the magnitude of the
angular momentum vector by the equation
|L| = h
_
( + 1)
and m is related to the z-component of the angular momentum vector by the
equation
L
2
z
() = h
2
m
2
() L
z
= hm
where m can take on all integer values from to +. In the case where = 0 (i.e.,
the angular momentum equal to zero) m is also zero as you would expect. In the
case where = 1, however, we have |L| = h

2 and L
z
= hm where m = 1, 0, +1.
This means that the z-component of the angular momentum can never be as great
as the magnitude of the angular momentum! The angular momentum vector can
never be completely lined up along the z-axis! Now, the angle that the total
6
angular momentum vector makes with the z-axis can be determined using the
denitions and the diagram shown below.
x
y

z
L
L
z
As can be seen,
cos =
L
z
L
or
cos =
m
_
( + 1)
When = 1, and m = 0 the angle is 90

. But when m = 1 we obtain

cos =
1

2
= 45

is the minimum value of . The angular momentum

vector precesses about the z-axis, maintaining the constant value of for a par-
ticular value of the quantum number m. You can see that as L becomes larger
(i.e., as becomes larger), the minimum value of the angle approaches zero.
Thus, for large quantum numbers, the angular momentum can be aligned with
the z-axis, as is the case in classical physics.
Continuing our discussion of the solution to the Hydrogen atom, one nds that
the solution to the radial equation, R(r), depends upon the quantum number
(and therefore ), and also upon another quantum number that arises from the
demand that the wave function be nite. This latter quantum number we will
designate as n. The rst few solutions to the radial wave equation are:
7
R
1,0
=
2
_
a
3
o
e
r/ao
R
2,0
=
1
_
2a
3
o
_
1
r
2a
o
_
e
r/2ao
R
2,1
=
1
_
24a
3
o
r
a
o
e
r/2a
o
Plots of the rst few solutions are shown on the next page, and on the following
page are the plots of the probability of nding an electron at a particular value
of the radius (independent of the angles and ). To obtain this latter function
one must integrate the radial wave function over all angles.
The general solution to the three-dimensional hydrogen atom is of the form
(r) = R
n,l
(r)Y
,m
(, )
where the values of the quantum numbers which are associated with realizable
wave functions are given by:
n = 0, 1, 2, 3, . . .
= 0, 1, 2, . . . , n 1
m +
Some representative diagrams are shown on the following pages which attempt to
illustrate the three-dimensional nature of the solutions.
8