Problem 6.

16
The most prominent feature of the hydrogen spectrum in the visible region is the red Balmer
Line, coming from the transition n=3 to n=2. First of all, determine the wavelength and
frequency of this line, according to the Bohr theory. Fine structure splits this line into several
closely spaced lines; the question is: How many, and what is their spacing? Hint: First
determine how many sublevels the n=2 level splits into and find E1fs for each of these, in eV.
Then do the same for n=3. Draw an energy level diagram showing all possible transition
from n=3 to n=2. The energy released (in the form of a photon) is ( E3 −E2 ) +∆ E , the first
part being common to all of them, and ∆ E (due to fine structure) verying from one transition
to the next. Find ∆ E (in eV) for each transition. Finally, convert to photon frequency, and
determine the spacing between adjacent spectral lines (in Hz) not the Frequency interval
between each line and the unperturbed line (which is, of course, unobservable), but the
frequency interval between each line and the nex one. Your final answer should take form,
“the red Balmer Line splits into (???) lines. In order of increasing frequency, they come from
the transitions (1) j= (???) to j= (???), (2) j= (???), and so on. The frequency spacing
between line (1) and line (2) is (???) Hz, the specing between line (2) and line (3) is (???) Hz.
And so on.
Answer:
We have transition from n=3 to n=2 to find λ and v we need to calculate
∆ E=hv → ∆ E=E3o+ Eo2
According to Bohr’s theory:
∆ E=Eo3 + E o2
1 1
¿ E1
( −
n23 n22 )
¿ E1 ( 19 − 14 )
E1=−13.6 eV

Then ∆ E=−13.6 ( 19 − 14 )=1.889 eV

6.62 ×10−34 −15
h= −19
=4.14 × 10 eV / s
1.6 × 10
∆E
∆ E=hv → v=
h
 1.889
v= −15
=4.56 ×1014 Hz
4.14 ×10
And the wavelength is:
c 3 ×10 8 −7
λ= = 14
=6.57 × 10 m
v 4.56 ×10
To calculate the fine structure
2
' ( En ) 4n
E =
fs
2mc 2
( )
3−
j+
1
2
1 3
For n=2⇒ l=0,1 ⇒ j= , we have 2 level due to the splitn=2
2 2
2
1 ' ( E2) 8
j= ⇒ E2=
2 2 mc 2
3−
1 1
+
2 2 ( )
E1 13.6
E 2= 2
= eV
n 4

' ( 13.6 )2
E= 2
2 6
( 3−8 )=5.66 ×10−5 eV
( 4 ) ( 2 ) ( 0.511 ×10 )
2
3 ' ( E2 ) 8
j= ⇒ E2=
2 2 mc 2
3−
3
+
2 2
1
( )
( 13.6 )2 8
E'2= 2 6
( 4 ) ( 2 ) ( 0.511 ×10 ) ( )
3− =−1.13× 10−5 eV
2
1 3 5
For n=3 ⇒ l=0,1,3 ⇒ j= , , we have 3 level splitting for n=3
2 2 2
2
1 ' ( E3) 12
j= ⇒ E3=
2 2 mc 2
3−
1 1
+
2 2 ( )
E1 13.6
E3 = 2
= eV
n 4
(13.6 )2
E'3 = 2 6
( 3−12 )=−2.01 ×10−5 eV
( 9 ) ( 2 ) ( 0.511 × 10 )
2
3 ' ( E3 ) 12
j= ⇒ E3=
2 2mc 2
3−
3 1
+
2 2 ( )
 ' (13.6 )2
E= 2
3 6
( 3−6 )=−6.7 ×10−6 eV
( 9 ) ( 2 ) ( 0.511 × 10 )
2
5 ( E3 ) 12
j= ⇒ E'3=
2 2mc 2
3−
5
+
2 2
1
( )
(13.6 )2
E'3 = 2 6
( 3−4 )=2.23 ×10−6 eV
( 9 ) ( 2 ) ( 0.511 × 10 )
Then, we have six transitions of energies:
∆ E=( E 03−E'3 ) −( E 02−E'2 )=( E 03−E02 ) + ( E'3−E '2 )

We need to calculate ( E '3−E'2 ) take ∆ E=( E '3−E'2 )

So we calculate ∆ E in every transition, then:
1 1
1. → ⇒ ( E'3−E '2)
2 2
2
' ( E3 ) 12
E= 3
2mc 2
( )
3−
j+
1
2
2
( E1 ) 12
¿ 2
( )
( 9 ) ( 2 ) ( 0.511× 10 ) 6
3−
j+
1
2
2
' ( E2 ) 8
E= 2
2mc 2
( )
3−
j+
1
2
2
( E1 ) 8
¿ 2
( )
( 4 ) ( 2 ) ( 0.511 ×10 ) 6
3−
j+
1
2

( 13.6 )2 1 1
∆ E 4= 6
( 2 ) ( 0.511 ×10 ) 9
2 (
( 3−12 )− 2 ( 3−8 )
4 )
¿ 3.6 ×10−5 eV
1 3
2. → ⇒ ∆ E=( E'3−E '2 )
2 2
( 13.6 )2 1 1
∆ E 1= 6
( 2 ) ( 0.511 × 10 ) 9
2
4 (
( 3−12 ) − 2 ( 3−4 )
)
¿−8.8 ×10−6 eV
3 1
3. → ⇒ ∆ E=( E'3−E '2 )
2 2
 ( 13.6 )2 1 1
∆ E 5= 6(
( 2 ) ( 0.511 × 10 ) 9
2
( 3−6 )− 2 ( 3−8 )
4 )
¿ 4.99 ×10−5 eV
3 3
4. → ⇒ ∆ E=( E'3 −E'2 )
2 2
( 13.6 )2 1 1
∆ E 2=
(
6
(2 ) ( 0.511 × 10 ) 9
2
( 3−6 )− 2 ( 3−4 )
4 )
¿ 4.6 × 10−6 eV
5 1
5. → ⇒ ∆ E=( E'3−E '2 )
2 2
( 13.6 )2 1 1
∆ E 6= 6(
( 2 ) ( 0.511 × 10 ) 9
2
( 3−4 )− 2 ( 3−8 )
4 )
¿ 5.4 ×10−5 eV
5 3
6. → ⇒ ∆ E=( E'3 −E'2 )
2 2
( 13.6 )2 1 1
∆ E 3=
(6
( 2 ) ( 0.511 × 10 ) 9
2
( 3−4 )− 2 ( 3−4 )
4 )
¿ 9.1 ×10−6 eV
1 3
The transition → has frequency less that the unpertubed line, and the other 5-transitions
2 2
have higher frequencies. Then the frequency spacing can be calculated as:
∆ E6 ∆ E5
v 6 → v 5= −
h h
1
¿ −15
( 5.4 ×10−5−4.99× 10−5 )
4.14 ×10
¿ 0.99 ×109 eV
∆ E5 ∆ E4
v5 → v 4 = −
h h
1
¿ −15
( 4.99 ×10−5−3.6 ×10−5 )
4.14 ×10
¿ 3.36 ×10 9 eV
∆ E4 ∆ E3
v 4 → v3 = −
h h
1
¿ −15
( 3.6 ×10−5−9.1 ×10−6 )
4.14 ×10
¿ 6.5 ×109 eV
 ∆ E3 ∆ E2
v3 → v 2= −
h h
1
¿ −15
( 9.1 ×10−6−4.6 × 10−6 )
4.14 ×10
¿ 1.09 ×109 eV
∆ E 2 ∆ E1
v 2 → v 1= −
h h
1
¿ −15
( 4.6 × 10−6 +8.8 ×10−6 )
4.14 ×10
¿ 3.24 ×10 9 eV