Lecture 8 -Title: Quantum Mechanical treatment of One-electron atoms : radial part

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In the previous lecture, we have solved the angular part of the Hamiltonian.
In this lecture, we will take up the radial part of the Hamiltonian.
We will also determine the total wavefunction of the Hydrogen atom and will calculate the
energy levels.

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Now, let us solve the radial part (Eqn. 8.8)
1 d 2 dR 2
Ze 2 ( + 1)
r
E
0
+
+
R=

r 2 dr dr 2
4 0 r
r2

Let us first evaluate the ground state (lowest energy) of hydrogen atom.
Assuming the ground state and taking = 0 , we get

1 d 2 dR 2
Ze 2
r
E
0
+
+

R =

r 2 dr dr 2
4 0 r
2 d 2R
dR 2
Ze 2
r
2
r
E
0
+
+
+

R =
dr 2
dr 2
4 0 r

1
r2

d 2 R 2 dR 2
Ze 2
E
0
+
+
+

R =
dr 2 r dr 2
4 0 r
.. Eqn. (21)

Let us try a solution R ( r ) = Ae

a0

, where A and a0 are constants.

dR ( r )
A r
d 2 R A r a0
e
=
e a0 ;
=
dr
a0
dr 2 a02
A r a0 2 A r a0 2 A
Ze 2 r a0
e
e

+ 2 E+
=
0
e
a02
ra0

4 0 r
1 2 E 2 Ze 2 2 1
2 + 2 +
=
0
2
a
a
r

4
0
0
0

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To satisfy this equation for any value of r ,
1 2 E
0
+ 2 =
a02

2
E=

2 a02
..Eqn. (22)

and

2 Ze 2 2
0
=
4 0 2 a0
a0
=

4 0 2 4 0 2
=
Ze 2
e2

Z 1]
[ for=
..Eqn. (23)

Let us calculate the values of a0 and Ground State Energy E ,

me m p
me + m p

9.109 1031 Kg
where=
me 9.109 1031 Kg

=
m p 1.672 1027 Kg

m p me
and

=
e 1.6 1019 Coul
2
1
= 8.988 109 nt m
Coul 2
4 0
= 1.055 1034 J sec= 0.6582 1015 eV sec

(1.055 10 )
(1.6 10 ) 9.109 10
34 2

a0 =

8.988 109

19 2

31

1.055 1.055
103434+19+19+319
8.988 1.6 1.6 9.109
o

=0.00531 108 m =0.529 1010 m =0.529 A

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Substituting value of a0 in Eqn. (8.22),

E=

2
2 a02

(1.055 10 )
=
2 9.109 10 ( 0.529 10 )
34 2

31

10 2

1.113 1068
5.098 1051

0.2183 1017
0.1364 10+2 =
=
=
13.6 eV
19
1.6 10
This is the lowest energy state of Hydrogen obtained also from Bohrs calculation.

Now let us calculate the general radial equation,

R=

r 2 dr dr 2
4 0 r
r2

The radial derivatives simplify if one factor 1 out from function R , taking
r

R (r ) =

u (r )
r
..Eqn. (24)

du
u
dR
= dr 2
dr
r
du
dR
r2
u
r
=
dr
dr
r

d 2 dR
d 2u du du

=
+
r
r

dr
dr dr
dr 2 dr
1 d 2 dR
d 2u
2
r
=
r

r dr dr
dr 2

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Substituting,
2
Ze 2 ( + 1) u ( r )
1 d u ( r ) 2
E
+
+
=
0
2

r dr 2
r2 r
4 0 r

d 2u ( r ) 2
Ze 2 ( + 1)
+
+
E
0
2
u (r ) =

dr 2
r
r

4
0

..Eqn. (25)
This is the Schrdinger equation for the particle in one dimension, restricted to r > 0 .
Rearranging

2
( + 1)
d u ( r ) 2 E 2 Ze

u ( r ) =0
dr 2
r 2
4 0 2 r
2

Veffective

This is a kind of potential ( for 0 ) with positive infinity at the origin, then negative potential
and going to zero at large distances. So the minimum of the potential is at some positive r .
For bound states of proton-electron system, E will be a negative quantity.

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Now, we will simplify by introducing dimensionless variable, such as

= + r
d = + dr
d 2 = 2 dr 2

2
Ze 2
2 d u ( r )
2 ( + 1)
E
0
+
+

u (r ) =
2 dr 2
4 0 r 2 r 2

2
2
Ze 2
2 2 d u ( )
2 ( + 1)
0

+ E +

u() =
d2
2
4 0 2
2

2
2 2 E ( + 1)
Ze 2
2 2 E d u ( )
+
+

u() = 0
2
d2
4 0 2 2
2 2

d 2u ( )
Ze 2 1 ( + 1)
1
+
+
+

u ( ) =0
d2
2
4 0 E

d 2u ( )
Ze 2 2 E 1 ( + 1)

1
+

u()
2
2
d2
4 0 E

Z e 2 1 ( + 1)
=
+
1
u()
2
2
2 0
Substituting 0 =

Z e2
, we get
2 0 2

d 2u ( ) 0 ( + 1)
=1 +
u()
d2

..Eqn. (26)

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Here, we understand the asymptotic behavior of solution of the equation 8.26.
Case-I: when is very large (at large separation between proton and electron), we can neglect
the terms in equation 8.26 and we get,
d 2u ( )
= u()
d2
The solution is of the type,

u=
( ) Ae + Be+
Since e becomes infinite for large , we take and hence,

u ( ) ~ Ae
Case-III: When is very small, then
d 2u ( )
d2

( + 1)

u()

[ Note 0]

d 2u ( )
The solution,
= C +1 + D
d2
Again, as 0 ; becomes infinite.
So we take, D = 0
So, for small ,

u ( ) ~ C +1

is the dominant term, so,

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So, we have established that the solution u ( ) decays as e at large distance and goes as +1
close to the proton (origin).
Now we write the general solution of equation as

u ( ) = +1e ( )
.....Eqn. (27)
where, ( ) we have to define.
Let us substitute u ( ) into the Eqn. (8.26)

d u()
d ( )
= +1e
+ ( + 1) e ( ) +1e ( )
d
d
d ( )

= e
+ ( + 1 ) ( )
d

and
d 2 ( )

d 2u ( )
d ( ) ( + 1)

e
=
+ 2 ( +1 )
+
2 ( + 1) + ( )
2
2
d
d
d

Substituting in Eqn. (8.26)

d ( ) ( + 1)

e
+ 2 ( +1 )
+
2 ( + 1) + ( )
2
d
d

( + 1)
= 1 0 +
e ()
2

2
d ()
d ( ) ( + 1)
( + 1)
2
1

+
+

+
1
+

(
)
(
)

( ) = 0
0
d2
d


d 2 ( )
d ( )

+ 2 ( +1 )
+ { 0 2 ( + 1)} ( ) =0
2
d
d

..Eqn. (28)

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Now, we have to solve this equation 8.28. Let us take a solution of the form,

( ) = Cj j
j =0

d ( )
= jC j j 1
d
j =0

So,

d 2 ( )
and
=
d2

j ( j 1) C
j =0

j 2

Putting back to Eqn. (8.27)

=j 0

j ( j 1) C j j 1 + 2 ( + 1) jC j j 1 2 jC j j + ( 0 2 ( + 1) ) C j j =
0
=j 0=j 0

=j 0

Shifting the summation of the j 1 terms

( j + 1) jC

j
j
j
j
0
j +1 + 2 ( + 1) ( j + 1) C j +1 2 jC j + ( 0 2 ( + 1) ) C j =

1
j=

0
1
j=
j=

0
j=

For, j = 1 , the first two terms becomes zero. So, we start from j = 0

=j 0

j ( j + 1) C j +1 j + 2 ( + 1) ( j + 1) C j +1 j 2 jC j j + ( 0 2 ( + 1) ) C j j =
0
=j 0=j 0

=j 0

j ( j + 1) C j +1 + 2 ( + 1)( j + 1) C j +1 2 jC j + ( 0 2 ( + 1) ) C j j =
0
j =0

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This is valid, if all the coefficients of j are zero.

j ( j + 1) C j +1 + 2 ( + 1)( j + 1) C j +1 2 jC j + ( 0 2 ( + 1) ) C j =
0

( 2 j + 2 ( + 1) ) 0 C
C j +1 =
( j + 1) ( j + 2 ( + 1) ) j
..Eqn. (29)
Let us examine the behavior at large j value. For large j value, we ignore ( + 1) and 0 , so,

2
C
( j + 1) j

C j +1 =

Taking the value C0 for j = 0

2
C1 = C0
1
2
22
=
C2 =
C1
C0
2
1 2
2
23
=
C3 =
C2
C0
3
1 2 3
2j
C j = C0
j!
Thus,

=
()

2j j

0 j!

C j j C0
=

=j 0=j

= C0 e 2

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Returning back in Eqn. (8.27), the general solution,
u ( ) = +1e ( )
= +1e C0 e 2
= C0 +1e
Again, the value of u ( ) increases exponentially for large and cannot be accepted. The
series has to terminate at finite number before reaching the large value of .
So, we should except, that at some finite value of j , Eqn. (8.29)

2 ( j + + 1) =
0
So, 0 should be an even integer.
We define, 0 = 2n
Z e2
= 2n
2 0 2
So, =

Z e2
4 0 2 n

and,

Z e2
2 E
=
4 0 2 n
2

Z 2 2e4
2 E
2 =
2

( 4 0 ) 4 n 2
E=

Z 2 e4

( 4 0 )

1
2
2 2 n

This is same energy as Bohr formula for Hydrogen putting Z = 1 .

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Substituting 0 = 2n in Eqn.8.29 this
C j +1 =
=

2 ( j + + 1) 2n

( j + 1) ( j + 2 ( + 1) ) j
2 ( n 1 j ) 2n

C
( j + 1)( 2 + j + 2 ) j

In fact, the solution of Eqn.8.28 is known as Associated Laguerre polynomials which is of the
form

( ) = L2n+11 ( 2 )

( 1)

2 j ( n + )!
j = 0 ( n j 1) ! ( 2 + j + 1) ! j !

So, the coefficients

( 1)

2 j ( n + )!
( n j 1)! ( 2 + j + 1)! j !
=

2 ( n 1 j )
( j + 1)( 2 + j + 2 )

which is same as before.

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In fact, rearranging Eqn. (8.28) we can get the solution as Associated Laguerre Polynomials of
the differential equation of the form,

d2 k
d k
Z
L Z + k +1 Z )
Ln ( Z ) + n Lkn ( Z ) =0
2 n ( ) (
dZ
dZ
Substituting Z = 2 in Eqn. (8.28), we get,

d ( Z ) 0
d2

+ ( + 1) ( Z ) =0
( Z ) + ( 2 + 1) + 1 Z
2
dZ
dZ
2

Here, =
k 2 + 1 , and

( + 1)
2
2n
= ( + 1) =n ( + 1)
2

n=

So the solution,
2 +1
=
( Z ) L=
Z
L2n+(1 +1) ( 2 )
n ( +1) ( )

In this case, the solution (27) has to be rearranged and we get,

+1

e L2n+(1 +1) ( 2 )

So,
2r
rRn ,=
( r ) u=
(r )
na0

+1

n a0

2r
L2n+(1 +1)

na0

2r 2 +1 2r
N n , e
Rn , ( r ) =

Ln ( +1)

na0
na0
r

n a0

.. Eqn. (30)
Here we have added the normalization constant N n , and absorbed the factor 2
power term of r .

na0

from the

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Now, we evaluate the normalization constant N n , from the relation,

Rn*, ( r ) Rn , ( r ) r 2 d = r1

Substituting,
na
N 0
2
2

2r

n a0

2r

na0

2+2

2 +1 2r 2r
Ln 1
d
=1
na0 na0

Here, we can use the orthogonality relation,

{( n + k )!}

e Z

L ( Z=
) L ( Z ) dZ

k +1 k
n

k
m

n!

( 2n + k + 1) m n

3
na0 2n {( n + ) !}
=1

2 ( n 1) !
3

So, we get, N n ,

2 ( n 1) !
=

3
na0 2n {( n + ) !}
3

So, N n ,

Normalized Radial Wavefunction,

2 ( n 1) ! r n a0 2r
2 +1 2r
Rn , ( r ) =
e

* Ln 1

3
na0 2n {( n + ) !}
na0
na0
3

.. Eqn. (31)
Some useful Associated Laguerre Polynomials
=
L10 ( Z ) 1=
;
L30 ( Z ) 6
L11 ( Z ) =
4 2Z
;
L13 ( Z ) =
96 24 Z
L12 ( Z ) = 3Z 2 18Z + 18

And the first few normalized radial wavefunction for Hydrogen,

Page-15
Following figures show the plots of the radial function of the hydrogen atom.

R1,0 ( r ) = 2a0 2 e
3

a0

Page-16

R2,0 ( r )
=

1 32
r r 2 a0
a0 1
e
2
2a0

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R2,1 ( r ) =

1 3 2 r r 2 a0
a0
e
a0
24

Page-18

R=
3,0 ( r )

2 32
2r
2r 2 r 3a0
a0 1
e
+
2
27
3a0 27 a0

Page-19

R3,1 ( r )
=

8
r r r 3a0
3
a0 2 1
e
27 6
6a0 a0

R3,2 ( r ) =

2
r
4
3 r
a0 2 2 e 3a0
a0
81 30

So the total wavefunction,

n , ,=
Rn , ( r ) ,m ( ) m ( )
m
From Eqn. (8.20) and (8.31),

2 ( n 1) ! r n a0 2r 2 +1 2r
=
e

Ln 1

3
na0 2n {( n + ) !}
na0
na0

n , , m

( 2 + 1) ( m )! P m Cos
)
(
4 ( + m ) !

.. Eqn. (32)
Here, n Principle Quantum Number
Azimuthal Quantum Number

m Magnetic Quantum Number

Recap
In this lecture, we have solved the radial part of the Hamiltonian.
We have also determined the total wavefunction of the Hydrogen atom.
The calculated energy levels depend on the principle quantum number n.
However, the total wavefunction of the electron is characterized by three quantum numbers,
namely n, l, ml.