Modern Physics.

Home Work 5

SOLUTION OF HOME WORK 5

1. Why are three quantum numbers needed to describe the state of a one-electron atom?

Solution.
The hydrogen atom is a three dimensional system, therefore only three quantum num-
bers are required.

2. Compare Bohrs theory with the Schrodinger treatment of electrons inside the H atom?

Solution. Bohrs model postulates that electrons orbit the nucleus in definite paths,
and are at fixed distances from the nucleus; whereas Schrodinger showed that electrons

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Modern Physics. Home Work 5

are really waves spread out in space. When one performs measurements on electronic
positions, the outcomes are spread out. However, the maximum likelihood of locating
the electron has some partial correspondence with Bohrs model. Furthermore, in
Bohrs model, the angular momentum takes up values l~ whereas in Schrodingers

new quantum theory, the angular momentum is quantized according to l(l + 1)~.

3. A particle of mass m moves in a three-dimensional box with edge lengths L1 ,L2 ,L3 .
Find the energies of the six lowest states if L1 =L, L2 =2L, and L3 =2L. Which of these
states are degenerate?

Solution.

The magnitude of the particles momentum in any direction is quantized as,

~
|px | = ~kx = n1 n1 = 1, 2, 3, . . .
L1
~
|py | = ~ky = n2 n2 = 1, 2, 3, . . .
L2
~
|pz | = ~kz = n3 . n3 = 1, 2, 3, . . .
L3

The allowed energies are,

E = (|px |2 + |px |2 + |px |2 )/2m

[( )2 ( )2 ( )2 ]
~2 2 n1 n2 n3
= + + ,
2m Lx Ly Lz

whereas we are also provided with the information, Lx = L, Ly = Lz = 2L. Now

suppose that,

~2 2
E0 = .
8mL2

Substituting the given values in our energy expression we obtain,

[( 2 ) ( 2 ) ( 2 )]
~2 2 n1 n2 n3
E = 2
+ 2
+
2m L 4L 4L2
[ ]
~2 2
= 2
4n21 + n22 + n23
8mL
= E0 [4n21 + n22 + n23 ].

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Modern Physics. Home Work 5

Choosing the quantum numbers n1 , n2 and n3 appropriately, helps us build the table
given below.

n1 n2 n3 E/E0 comments
1 1 1 6 ground state
1 1 2 9 first excited state
1 2 1 9 first excited state
1 2 2 12 second excited state
1 3 1 14 third excited state
1 1 3 14 third excited state
2 1 1 18 fourth excited state
1 4 1 21 fifth excited state
1 1 4 21 fifth excited state
2 1 2 21 fifth excited state
2 2 1 21 fifth excited state

The table shows the lowest energy states, with relative energies,

E
= 6, 9, 12, 14, 18, 21.
E0

The first, third and fifth excited states are two, two and four-fold generate respectively.

4. (a) Determine the quantum numbers l and ml for the He+ ion in the state correspond-
ing to n=3. (b) What is the energy of this state?

Solution.

The atomic number Z = 2 for He+ .

(a) For n = 3, l can have the values of 0, 1, 2.

l = 0 ml = 0
l = 1 ml = 1, 0, +1
l = 2 ml = 2, 1, 0, +1, +2

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Modern Physics. Home Work 5

(b) In Bohrs model, the energy levels corresponding to the principal quantum number
n are,
Z 2
En = (13.6) eV.
n2

For n = 3
Z 2
E3 = (13.6)
32
= 6.04 eV.

5. The radial part of the wave function for the hydrogen atom in the 2p state is given by

R2p (r) = Arer/2a0

where A is a constant and a0 is the Bohr radius. Using this expression, calculate the
average value of r for an electron in this state.

Solution.
The average distance of the electron from the nucleus is found by weighting each
possible distance with the probability that the electron will be found at that distance,

r = rP (r)dr (1)
0

where the radial probability density is,

P (r) = r2 |R(r)|2 .

We can first find the constant A by imposing the normalization condition on the radial
part,

P (r)dr = r2 |R(r)|2 dr
r=0
0
= A2 r4 er/a0 dr
r=0

= A 2
r4 er/a0 dr.
r=0

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Modern Physics. Home Work 5

Making the substitutions, r/a0 = z, r = a0 z and dr = a0 dz, the above integral

becomes,

A 2
(a0 z)4 ez a0 dz
z=0

= A2 a50 z 4 ez dz
z=0
2 1
= A a50 4! = 1 = A = 5/2 , (2)
a0 2 6

where we have used the standard result z=0
z n ez dz = n! in the last step of the
evaluation.

We may now use Equation (1) to calculate the average distance,

r = A2 r5 er/a0 dr
r=0

= A 2
(a0 z)5 ez a0 dz

z=0
2 6
= A a0 z 5 ez dz
z=0
2 6
= A a0 5! inserting the value of A,
a60 5!
= = 5 a0 . (3)
a50 4!

6. Compare the most probable distances of the electron from the proton in the hydrogen
2s and 2p states with the radius of the second Bohr orbit in hydrogen, 4a0 .
Solution.

The most probable distance is the value of r which maximizes the radial probability
density P (r) = |rR(r)|2 . Since P (r) is largest where rR(r) reaches its maximum, we
can look for the most probable rmax distance by setting
d{rR(r)}
=0
dr
using the functions R(r) from the provided Table.

For the 2s state of hydrogen, the condition for a maximum is,

[ { ( )3/2 }]
d 1 Z Zr Zr/2a0
0 = r (2 )e
dr 4 2 a0 a0
( )3/2 {( ) }
1 Z d Zr2 r/2a0
0 = 2r e .
4 2 a0 dr a0

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Modern Physics. Home Work 5

For Z = 1,
( )3/2 {( ) }
1 1 d r2 r/2a0
0 = 2r e
4 2 a0 dr a0
( )3/2 {( ) ( )}
1 1 2r r/2a0 er/2a0 r2
0 = 2 e 2r
4 2 a0 a0 2a0 a0
{( ) ( 2
)}
2r 1 r
0 = er/2a0 2 2r
a0 2a0 a0
{( ) ( 2
)}
2r 1 r
0 = 2 2r
a0 2a0 a0
2
2r r r
0 = 2 + 2
a0 a0 2a0
3r r2
0 = 2 +
a0 2a20
0 = 4a20 6ra0 + r2 .

Using the quadratic formula to calculate the possible values of rmax ,

(6a0 ) (6a0 )2 4(4)(a0 )2
rmax =
2(1)

6a0 36a0 16a20
2
=
2
6a0 20a20
=
2
r = (3 5)a0 , = 0.7 a0 , 5.3 a0 .

The two possible solutions indicate the presence of two humps in the radial probability
density for the 2s orbital. (Carefully observe the densities on page 245 of
Eisbergs book!)

For the 2p state of hydrogen, a similar analysis yields,

[ { ( )3/2 }]
d Zr Z Zr/2a0
0 = r e
dr 3a0 2a0
{ 2 r/2a0 }
d r e
0 =
dr 23/2 a5/2 3
{ 2
}o
r
0 = 2r er/2a0
2
with the obvious roots r = 0 (a minimum) and r = 4 (a maximum). Thus, the most
probable distance for the 2p state is r = 4a0 , in agreement with the simple Bohr model.

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Modern Physics. Home Work 5

The L shell in Bohrs model is at a distance of 22 a0 = 4a0 from the nucleus, which
matches the most probable distance of a 2p electron, computed using a wavefunction
approach.

Due date: December 05, 2011 7