Hydrogen Atom: Taken from Modern Physics by A.

Beizer, Chapter 6

Schrodinger Equation for the hydrogen atom

System has one proton and one electron. Given that the nucleus (proton) is much heavier, we will assume it to
be stationary, and hence the wave function of the system is given by the wave function of the electron

(x, y, z).

The Schrodinger equation for the electron, experiencing a electrostatic potential the stationary nucleus (at
origin, charge

+e)

at a distance of

~2

2m

r=


(x2 + y 2 + z 2 )is

2 2 2
+
+
x2
y 2
z 2

thus given by:

e2
+
40 r



= E.

(1)

The spherical symmetry of the system suggests using spherical polar coordinates. The spherical polar coordinates

(r, , )

are related to the Cartesian coordinates in the following fashion:

p
x2 + y 2 + z 2
,


= cos1 2 z 2 2
,

x +y +z

= tan1

y
x

Length of position vector

(2)

angle between z-axis and position vector

(3)

, angle between the x-axis and the projection of position vector onto x-y plane
(4)

z
(r, , )
r

x
Figure 1: Spherical polar system, from Wikipedia (http://en.wikipedia.org/wiki/Spherical_coordinate_system)

In the spherical polar coordinates, the

2 operator needs to be appropriately transformed, and the Schrodinger

equation becomes:

1
r2 r


r

which after multiplying with

sin2

r2

+ 2
r sin

r2 sin2

sin


+

1
e2
2 2m
+
(E
+
) = 0
2
~2
40 r
r2 sin 2

becomes


+ sin




2 2mr2 sin2
e2
sin
+
+
(E +
) = 0.
2
2

~
40 r

We will ASSUME and ATTEMPT the separation of variables

sin
r
2


r

2 R

+ sin

(5)

sin


R +

(r, , ) = R(r) () (),

(6)

which gives us

2
2mr2 sin2
e2

R
+
(E
+
)R = 0,
2
~2
40 r

(7)

which upon division by

sin
r
2


r

2 R

R,


gives us:

+ sin
R

sin

1
e2
1
2
2mr2 sin2

(E
+
+
+
) = 0.

~2
40 r
2
2

We note that the LHS has 4 terms; (a) the third term (i.e.
(b) all other term involves other variables

and

1
) involves only one variable

and do not involve

(8)

alone AND

We sill split the equation into to parts,

by rearranging the this third term to RHS as:

sin2





e2
1
R
1

1
2mr2 sin2
2
(E +
r2
+ sin
sin
+
)= 2
2
r
R

~
40 r

(9)

which has the form:

f (r, ) = g()

(10)

which can only be true if both LHS and RHS are both equal to the same constant. We will assume that this
constant is

m2l ,

we will show (immediately below) why this has to be positive.

The RHS of Eq. 9 is a bit easier to tackle, and we have:

and since the variable

With

= Aeiml ,

1
2
= m2l = () = Aeiml ,
2

is periodic, i.e. and +2 are the same point (see Fig.1), we require () = (+2 ).

this gives us:

ei2ml = 1,

which tells us that

ml = 0, 1, 2

2
constant were not positive: i.e ml we would have solutions of type

ml

. Also note that if the

, which would mean

ml = 0

alone,

and precluding all OTHER solutions.

The LHS of Eq. 9 gives us:

sin2

which upon dividing by

we have:

r2

R
r

sin2

1
R r

+ sin
R


sin

1
2mr2 sin2
e2
+
(E +
) = m2l
2

~
40 r

and rearrangement so that all terms with

are on one side and with

(11)

on other,





2mr2
e2
m2l
1

2 R
r
+
(E +
)=

sin
r
~2
40 r

sin2 sin

(12)

which is of the form:

f (r) = g()
so that both have to be constants. We will call the constant

l(l + 1),

motivation for this will be evident below.

So we now have two equations:



1

m2l

sin

= l(l + 1)

sin2 sin


1
R
2mr2
e2
r2
+
) = l(l + 1)
(E +
2
R r
r
~
40 r

(13)

(14)

which we will rearrange to show the features:


 

1

m2l
sin
+ l(l + 1)
=0
sin

sin2

 


2mr2
e2
l(l + 1)
2 R
r
+
(E +
)
R=0
r
r
~2
40 r
r2

(; l, ml ) = l,ml ()

R(E, r; l)

E quantisation
=

Rn,l (r)

(15)

(16)

and we have already shown that

ml ().

(17)

Combining all things, we see that the total wave function has the following form:

(r, , ) = Rn,l (r) l,ml () ml ()

with three quantum numbers:

n, l

and

ml .

For other information look at the textbook mentioned.

(18)