Chapter 4 Atomic Structure (PP 96-125)

CHAPTER 04 ATOMIC STRUCTURE 96
CHAPTER 4
ATOMIC STRUCTURE

BOHRS THEORY OF HYDROGEN ATOM
Example 4-1
Determine the radius of the first orbit of the hydrogen atom.
Solution
The radius of electron in n
th
orbit of hydrogen atom is given by

k me
h n
r
n 2 2
2 2
4
=
) 10 988 . 8 ( ) 10 602 . 1 )( 10 109 . 9 ( 4
) 10 626 . 6 ( ) 1 (
9 2 19 19 2
2 34 2
1

r
53 . 0 10 287 . 5
11
1
=

m r
Example 4-2
Find the value of quantum number n for a hydrogen atom
that has an orbital radius of 847 pm.
Solution
The radius of in n
th
orbit of hydrogen atom is given by

2 11
10 3 . 5 n r
n
= in metres
4
10 3 . 5
10 847
10 3 . 5
11
12
11
=
n
r
n the desired quantum
number.
Example 4-3
Determine the speed of electron in 10
th
orbit of hydrogen
atom. B.U. B.Sc. (Hons.) 1984A
Solution
The velocity of electron in n
th
orbit of hydrogen atom is given
by

nh
e k
v
n
2
2
=
s m v / 10 187 . 2
) 10 626 . 6 )( 10 (
) 10 602 . 1 )( 10 988 . 8 ( 2
5
34
2 19 9
10
=

the desired speed.

Example 4-4
Find the de Broglie wavelength of an electron in the n = 3
orbit of hydrogen atom. In what region of the spectrum
would a photon of the same wavelength be classified?
Solution
The velocity of electron in n
th
orbit of hydrogen atom is given
by
h n
e k
v
n
2
2
= or
h
e k
v
3
2
2
3
= for n = 3.
The de Broglie wavelength is defined as

2
2
3
2
3
e k m
h
v m
h
p
h
= = =
2 19 9 31
2 34
) 10 602 . 1 ( 10 988 . 8 )( 10 109 . 9 ( 2
) 10 626 . 6 ( 3

10 10 977 . 9
10
=

m
The photon of this wavelength belongs to X-ray region.
Example 4-5
Calculate the frequency of electron in the first Bohr orbit of
hydrogen atom. B.U. B.Sc. 2004A
Solution
The velocity of electron in terms of radius is given by

r m
nh
v
2
=
The orbital frequency is given by
f = (speed of electron) (circumference of orbit)

2 2
4 2
1
2 mr
nh
r r m
nh
f

= =
But
k me
h n
r
2 2
2 2
4
= therefore

(
=
(
=
3 3
2 4 2
2
2 2
2 2
2
4 4
4 h n
k me
h n
k me
m
nh
f

3 34 3
2 9 4 19 31 2
) 10 626 . 6 ( ) 1 (
) 10 988 . 8 ( ) 10 602 . 1 )( 10 109 . 9 ( 4

=

f

15
10 577 . 6 = Hz

Example 4-6
On the average, an atom will exist in an excited state for
8
10
second, before it makes a downward transition and

emits a photon. Assuming that the electron in hydrogen is in
the state n = 2, how many revolutions about the nucleus are
made before the electron jumps to the ground state?
Solution
The time period T of electron in n
th
orbit is given by

2 4 2
3 3
4
1
k me
h n
f
T
= =
2 9 4 19 31 2
34 3
) 10 988 . 8 ( ) 10 602 . 1 )( 10 109 . 9 ( 4
) 10 626 . 6 ( ) 2 (

T
s T
15
10 216 . 1

=
Number of revolutions completed by electron is given by
6
15
8
10 224 . 8
10 216 . 1
10
=
period Time
state excited in Time
Revolutions
Example 4-7
Show that the energy of electron in n
th
for hydrogen atom is
given by
2
6 . 13
n
E
n
= eV.
Solution
The energy of electron in n
th
orbit is given by

2 2
2 4 2
2
h n
k me
E
n
= in joules

2 2
2 3 2
2
h n
k me
E
n
= in eV

2 34 2
2 9 3 19 31 2
) 10 626 . 6 (
) 10 988 . 8 ( ) 10 602 . 1 )( 10 109 . 9 ( 2

=
n
E
n

2
6 . 13
n
E
n
= in eV
Example 4-8
Calculate the binding energy of the hydrogen atom in the
first excited state.
Solution
th
orbit is given by

2
6 . 13
n
E
n
= in eV
For first excited state we substitute n = 2, therefore
4 . 3
) 2 (
6 . 13
2 2
= = E eV
Hence the binding energy of the hydrogen atom in the first
excited state is 3.4 eV.
Example 4-9
Calculate the energy of the electron for first two excited
states of hydrogen atom. What will be the wavelength of
emitted (or absorbed) radiation if an electron makes a
transition between these two states?
Solution
(a) The energy of electron in n
th
orbit is given by

2
6 . 13
n
E
n
= in eV
The energy of the first two excited states can be calculated by
substituting n = 2 and n = 3 respectively. Hence
eV E n 4 . 3
) 2 (
6 . 13
, 2
2
2
= = =
eV E n 51 . 1
) 3 (
6 . 13
, 3
2
3
= = =
(b)Now
hc
h E E = =
2 3

) 10 602 . 1 )}( 4 . 3 ( 51 . 1 {
) 10 998 . 2 )( 10 626 . 6 (
19
8 34
2 3
=
E E
hc

m
7
10 561 . 6

= or 6561
Example 4-10
Calculate the first, second and third excitation energies for
hydrogen atom.
Solution
th
orbit is given by

2
6 . 13
n
E
n
= in eV
Now , 1 = n eV E 6 . 13 ) 1 /( ) 6 . 13 (
2
1
= =
, 2 = n eV E 4 . 3 ) 2 /( ) 6 . 13 (
2
2
= =
, 3 = n eV E 51 . 1 ) 3 /( ) 6 . 13 (
2
3
= =
, 4 = n eV E 85 . 0 ) 4 /( ) 6 . 13 (
2
4
= =
Let
1,
2
and

3
be the first, second and third excitation
energies of the hydrogen atom, then

1
= eV E E 2 . 10 ) 6 . 13 ( 4 . 3
1 2
= =

2
= eV E E 09 . 12 ) 6 . 13 ( 51 . 1
1 3
= =

3
= eV E E 75 . 12 ) 6 . 13 ( 85 . 0
1 4
= =
Example 4-11
Calculate the value of Rydberg constant for hydrogen atom.
Solution
The Rydberg constant is defined by

3
4 2 2
2
ch
me k
R

=
3 34 8
4 19 31 2 9 2
) 10 626 . 6 )( 10 998 . 2 (
) 10 602 . 1 )( 10 109 . 9 ( ) 10 988 . 8 ( 2

=

R

1 7
10 097 . 1

= m R
Example 4-12
The wavelength of the first line of Lyman series of hydrogen
atom is 1216 . Calculate the wavelength of third line.
B.U. B.Sc. 1990A
Solution
The wavelength of different members of the Lyman series of
hydrogen atom is given by

(
=
2 2
1
1
1 1
n
R
n
, n = 2,3,4,.
For the first member n = 2 , therefore

4
3
2
1
1
1
1216
1
2 2
R
R =
(
=

) 1216 ) 3 (
4
= R =
912
1
=
-1

For the third member n = 4 and formula for Lyman series
becomes
4864
5
912
1
16
15
16
15
4
1
1
1 1
2 2
3
= = =
(
=
R
R

8 . 972
5
4864
3
= =
Example 4-13
The wavelength of the first line of Lyman series of hydrogen
atom is 1216 . Calculate the wavelength of 5
th
line.
B.U. B.Sc. 1992A
Solution
The wavelength of different members of the Lyman series of
hydrogen atom is given by

(
=
2 2
1
1
1 1
n
R
n
, n = 2,3,4,.
For the first member n = 2 , therefore

4
3
2
1
1
1
1216
1
2 2
R
R =
(
= or
) 1216 ) 3 (
4
= R
912
1
=
-1

For the fifth member n = 6 and formula for Lyman series
becomes
32832
35
912
1
36
35
36
35
6
1
1
1 1
2 2
3
= = =
(
=
R
R

938
35
32832
3
= =
Example 4-14
The wavelength of the first member of Balmer series of the
hydrogen atom is 6563 . Calculate the wavelength of the
first member of Lyman series in the same spectrum.
B.U. B.Sc. 2009A
Solution
The formula for Balmer series of hydrogen atom is

(
=
2 2
1
2
1 1
n
R
, n = 3,4,5, . . .
For first member of this series we substitute n = 3

36
5
3
1
2
1 1
2 2
1
R
R =
(

R 5
36
1
= (1)
The Lyman series is given by

(
=
2 2
1
1
1 1
n
R
, n = 2,3,4, . . . .
For first member of this series we substitute n = 2

4
3
2
1
1
1 1
2 2
1
R
R =
(
=

R 3
4
1
= (2)
Divide Eq(2) by Eq(1)

27
5
36
5
3
4
1
1
= |
\
|
|
\
|
=
R
R

37 . 1215
27
) 6563 ( 5
27
5
1
1
= = =

Example 4-15
Calculate the longest and shortest wavelength i.e. series
limit of the Lyman series.
Solution
The Lyman series is given by

(
=
2 2
1
1
1 1
n
R
, n = 2, 3, 4 . . .
For longest wavelength, substitute n = 2

4
3
2
1
1
1 1
2 2
R
R =
(

R 3
4
=
1215 10 5 . 121
) 10 097 . 1 ( 3
4
9
7
= =
=

m
For series limit, substitute = n
R R
n
R =
(
=
(
=
2 2 2
) (
1
1
1
1
1 1

912 10 912
10 097 . 1
1 1
10
7
= =
= =

m
R

Example 4-16
Calculate the longest wavelength in Balmer series. Also find
the value of the shortest wavelength. B.U. B.Sc. 1988S
Solution
The formula for Balmer series of hydrogen atom is

(
=
2 2
1
2
1 1
n
R
, n = 3,4,5,.
Substitute n = 3

36
5
3
1
2
1 1
2 2
R
R =
(

6563 10 563 . 6
) 10 097 . 1 ( 5
36
5
36
7
7
= =
= =

m
R

Substitute = n in above formula

4
1
2
1 1
2 2
R
R =
(

3646 10 646 . 3
10 097 . 1
4 4
7
7
= =
= =

m
R

The desired longest and shortest wavelengths are 6563 and
3636 respectively.
Example 4-17
Calculate the longest and shortest wavelength i.e. series
limit of the Paschen series. . B.U. B.Sc. 1991A
Solution
The formula for Paschen series of hydrogen atom is

(
=
2 2
1
3
1 1
n
R
, n =4,5,6, . . .
Substitute n = 4

144
7
4
1
3
1 1
2 2
R
R =
(

) 10 097 . 1 ( 7
144
7
144
7
= =
R

18750 1875 10 875 . 1
6
= = =

nm m
Substitute = n in above formula

9
1
3
1 1
2 2
R
R =
(

7
10 097 . 1
9 9
= =
R

8204 4 . 820 10 204 . 8
7
= = =

nm m
The desired longest and shortest wavelengths are 1875 nm and
820.4 nm respectively.

Example 4-18
Determine the largest wavelength when excited electron
make transition to n = 4 level. K.U. B.Sc. 2001
Solution
The wavelength of the emitted photon will; be the longest when
electron jumps from n = 5 to n = 4. Hence

400
9
5
1
4
1 1
2 2
R
R =
(

) 10 097 . 1 ( 9
400
9
400
7
= =
R

nm m 4051 10 051 . 4
6
= =

Note that this is the longest wavelength in Brackett series of
Hydrogen atom.
Example 4-19
Compute the first three wavelengths for the Paschen series
of hydrogen. In what region of the spectrum do the lines of
Paschen series lie?
Solution
The formula for Paschen series of hydrogen atom is

(
=
2 2
1
3
1 1
n
R
, n =4,5,6, . . .
Substitute n = 4 ,
144
7
4
1
3
1 1
2 2
1
R
R =
(

R 7
144
1
=
) 10 097 . 1 ( 7
144
7
=
nm m 1875 10 875 . 1
6
1
= =

Substitute n = 5 ,
225
16
5
1
3
1 1
2 2
2
R
R =
(

nm m
R
1282 10 282 . 1
) 10 097 . 1 ( 16
225
16
225
6
2
7
2
= =
= =

Substitute n = 6 ,
12 6
1
3
1 1
2 2
3
R
R =
(

nm m
R
1094 10 094 . 1
10 097 . 1
12 12
6
7
3
= =
= =

The wavelengths of desired lines are 1875 nm, 1282 nm and
1094 nm. These lines lie in the infrared region of the spectrum.
Example 4-20
Find the wavelength of the spectral line corresponding to
the transition in hydrogen atom from n = 6 to n = 3 state
where
7
10 097 . 1 = R m
-1
. B.U. B.Sc. 1991S
Solution
The desired line is the third line in Paschen series. The Paschen
series is given by

(
=
2 2
1
3
1 1
n
R
, n =4,5,6, . . .
Substitute n = 6

12 6
1
3
1 1
2 2
R
R =
(

7
10 097 . 1
12 12
= =
R

10939 9 . 1093 10 0939 . 1
6
= = =

nm m

Example 4-21
In the hydrogen atom, an electron experiences a transition
from a state whose binding energy is 0.54 eV to another
state whose excitation energy is 12.2 eV. (a) What are the
quantum numbers for these states? (b) Compute the
wavelength of the emitted photon. (c) To what series does
this line belong? K.U. B.Sc. 2008
Solution
The binding energy of the electron is given by

2
6 . 13
n
E
n
= in eV
(a)The above equation can be rewritten as

n
E
n
6 . 13
=
Now 54 . 0 =
n
E eV, therefore 5
54 . 0
6 . 13
= = n .
The binding energy 0.54 eV corresponds to the state n = 5. Note
that the binding energy of the state n = 1 is 13.6 eV. As the
excitation energy is given as 10.2 eV, therefore
eV E
n
4 . 3 2 . 10 6 . 13 = =
Hence 2
4 . 3
6 . 13
= = n
i.e. the given excitation energy corresponds to state n = 2.
(b)
hc
eV E E = = = 86 . 2 54 . 0 4 . 3
5 2

eV
hc
86 . 2
=
m
7
19
8 34
10 336 . 4
) 10 602 . 1 )( 86 . 2 (
) 10 998 . 2 )( 10 626 . 6 (

=
4336 = the wavelength of the emitted photon.
(c) As the wavelength of the emitted photon is in the visible
region, therefore it belongs to Balmer series of the hydrogen
atom.

Example 4-22
A collection of hydrogen atoms in the ground state is
illuminated with ultraviolet light of wavelength 59.0 nm.
Find the kinetic energy of the emitted electron.
Solution
The energy of the incident photon is given by
J
c h
E
18
9
8 34
10 367 . 3
10 0 . 59
) 10 998 . 2 )( 10 626 . 6 (

= =

eV eV E 0 . 21
10 602 . 1
10 367 . 3
19
18
=

The energy needed to separate the electron from hydrogen atom
is given by
eV E 6 . 13
1
=
The kinetic energy of the emitted electron will be
eV E E K 4 . 7 6 . 13 0 . 21
1
= = =


4-2 HYDROGEN-LIKE ATOMS
Example 4-23
How much energy is required to remove the electron from a
singly ionized helium atom (He
+1
) in its ground state?
Solution
th
orbit for hydrogen-like atom is
given by
eV in
n
Z
h n
Z k me
E
n
2
2
2 2
2 2 4 2
) 6 . 13 ( 2
= =

Now n = 1 and Z = 2, therefore the desired energy is
eV E 4 . 54
) 1 (
) 2 )( 6 . 13 (
2
2
1
= =
Example 4-24
Apply the Bohrs theory to He
+
and calculate for n = 1
(a) the radius, (b) the frequency of revolution, (c) the linear
speed of the electron, (d) the total energy of the electron, (d)
the angular momentum and (e) the ratio v/c, and (f) decide
whether the classical treatment can be used or not.

Solution
(a) The radius of n
th
orbit of electron in hydrogen-like atom is
given by
Z
n
e Z m k
h n
r
n
2 11
2 2
2 2
) 10 287 . 5 (
4
= =

Substitute n = 1, Z = 2 in above equation
m r
11
2 11
1
10 644 . 2
2
) 1 )( 10 287 . 5 (

=
(b) The orbital frequency of the electron in hydrogen-like atom
is given by

3 3
4 2 2 2
4
h n
e Z k m
f
n
=

) 10 626 . 6 ( ) 1 (
) 10 602 . 1 ( ) 2 )( 10 988 . 8 )( 10 109 . 9 ( 4
34 3
4 19 2 9 31 2
1

=

f
Hz
16
10 631 . 2 = the desired frequency.
(c) The velocity of electron in n
th
orbit of hydrogen-like atom is
given by

nh
e Z k
v
n
2
2
=
) 10 626 . 6 )( 1 (
) 10 602 . 1 )( 2 )( 10 988 . 8 ( 2
34
2 19 9
1

=

v
s m/ 10 375 . 4
6
1
=
(d) The energy of electron in nth orbit for hydrogen-like atom is
given by
eV in
n
Z
h n
Z k me
E
n
2
2
2 2
2 2 4 2
) 6 . 13 ( 2
= =

eV E 4 . 54
) 1 (
) 2 )( 6 . 13 (
2
2
1
= =
(e) The angular momentum of electron in first orbit is given by
) 10 644 . 2 )( 10 375 . 4 )( 10 109 . 9 (
11 6 31
1 1 1

= = r v m L

1 2 34
10 054 . 1

= s m kg
(f) 015 . 0
10 998 . 2
10 375 . 4
8
6
=
=
c
v
As the ratio (v/c) is small i.e. v
is very small as compared with c, therefore classical treatment is
applicable.
Example 4-25
Determine the radius of the second Bohr orbit for doubly
ionized Lithium.
Solution
The radius of n
th
orbit for Hydrogen-like atom is given by

Z
r n
r
n
1
2
=
where 53 . 0
1
= r is the radius of the first Bohr orbit of
Hydrogen atom. Hence
706 . 0
3
) 53 . 0 ( ) 2 (
2
2
= = r
Example 4-26
How much energy is required to remove the electron from a
doubly ionized lithium atom (Li
+2
) in its ground state?
Solution
th
given by
eV in
n
Z
h n
Z k me
E
n
2
2
2 2
2 2 4 2
) 6 . 13 ( 2
= =

Now n = 1 and Z = 3, therefore the desired energy is
eV E 4 . 122
) 1 (
) 3 )( 6 . 13 (
2
2
1
= =
Example 4-27
(a) Compute the first and second excitation potentials for
singly ionized helium atom. (b) What wavelengths are
emitted when the He
+
returns to the ground state from these
excited states?
Solution
th
given by
eV in
n
Z
h n
Z k me
E
n
2
2
2 2
2 2 4 2
) 6 . 13 ( 2
= =

eV
n n
2 2
2
4 . 54 ) 2 )( 6 . 13 (
= = for He
+

Now n = 1 , eV E 4 . 54
) 1 (
4 . 54
2
1
= =
n = 2 , eV E 6 . 13
) 2 (
4 . 54
2
2
= =
n = 3 , eV E 04 . 6
) 3 (
4 . 54
2
3
= =
Let
1
and

2
be the first and second excitation energies of the
He
+
atom, then

1
= eV E E 8 . 40 ) 4 . 54 ( 6 . 13
1 2
= =

2
= eV E E 46 . 48 ) 4 . 54 ( 04 . 6
1 3
= =
The desired excitation potentials are 40.8 V and 48.46 V.
(b) Now
1
1
hc
=
or
) 10 602 . 1 )( 8 . 40 (
) 10 998 . 2 )( 10 626 . 6 (
19
8 34
1
1

= =
hc

304 10 039 . 3
8
1
=

m

2
2
hc
=
or
) 10 602 . 1 )( 46 . 48 (
) 10 998 . 2 )( 10 626 . 6 (
19
8 34
21
2

= =
hc

256 10 559 . 2
8
1
=

m
Example 4-28
Determine the wavelength of the first two lines of singly
ionized helium that corresponds to the first two lines of the
Balmer series.
Solution
The formula for Balmer series of hydrogen-like atom is

(
=
2 2
2
1
2
1 1
n
Z R
, n = 3,4,5,..
For singly ionized helium Z = 2 and above equation becomes

(
=
2 2
1
2
1
4
1
n
R
, n = 3,4,5,..
The desired wavelengths are calculated by substituting n = 3
and n = 4 respectively in above relation. Now

9
5
3
1
2
1
4
1
2 2
1
R
R =
(

1641 10 641 . 1
) 10 097 . 1 ( 5
9
5
9
7
7
1
= =
= =

m
R

4
3
4
1
2
1
4
1
2 2
2
R
R =
(

1215 10 215 . 1
) 10 097 . 1 ( 3
4
3
4
7
7
2
= =
= =

m
R

Example 4-29
Calculate the wavelengths of first two lines of the Balmer
series of triply ionized Beryllium (Z = 4).
Solution
The formula for Balmer series of Hydrogen-like atom is
(
=
2 2
2
1
2
1 1
n
Z R
, n = 3,4,5,..
For present case Z = 4 , therefore
(
=
2 2
2
1
2
1
16
1
n
Z
, n = 3,4,5,..
Now n = 3,
9
20
3
1
2
1
16
1
2 2
1
R
R =
)
`

nm m
R
0 . 41 10 10 . 4
) 10 097 . 1 ( 20
9
20
9
8
7 1
= =
= =

n = 4, R R 3
4
1
2
1
16
1
2 2
2
=
)
`

nm m
R
4 . 30 10 04 . 3
) 10 097 . 1 ( 3
1
3
1
8
7 2
= =
= =

Hence the wavelengths of the first two lines of the Balmer
series of triply ionized Beryllium are 41.0 nm and 30.4 nm
respectively.
Example 4-30
An atom of tungsten has all of its electrons removed except
one. (a) Calculate the ground-state energy for this one
remaining electron. (b) Calculate the energy and wavelength
of the radiation emitted when this electron makes a
downward transition from n = 2 to n = 1. (c) In what portion
of the electromagnetic spectrum is this photon?
Solution
(a)The energy of electron in n
th
given by
eV in
n
Z
h n
Z k me
E
n
2
2
2 2
2 2 4 2
) 6 . 13 ( 2
= =

For tungsten Z = 74, therefore

keV
n
eV
n n
E
n
2 2
4
2
2
5 . 74 10 44736 . 7 ) 74 )( 6 . 13 (

= =
keV E 5 . 74
1
= the desired ground state energy.
(b) When electron makes a downward transition from n = 2 to
n = 1, the energy E of the emitted photon is given by
keV keV keV E E E 9 . 55 875 . 55
1
1
2
1
5 . 74
2 2
1 2
=
(
= =
The wavelength of the emitted photon is calculated from the
relation
) 10 602 . 1 )( 10 875 . 55 (
) 10 998 . 2 )( 10 626 . 6 (
19 3
8 34

= =
E
hc

222 . 0 10 219 . 2
11
=

m
(c) The emitted photon belongs to X-rays.


4-3 THE FRANK-HERTZ EXPERIMENT
Example 4-31
In Franck-Hertz experiment the ionization potential of
sodium is 5.13 V. Calculate the velocity of the electron.
Solution
The kinetic energy of the electron is given by
Ve v m =
2
2
1

1 6
31
19
10 343 . 1
) 10 109 . 9 (
) 10 602 . 1 )( 13 . 5 ( 2 2

= = s m
m
Ve
v

Example 4-32
What will be the minimum energy of electron to excite
2536 spectral line of mercury in a Franck-Hertz
experiment?
Solution
The minimum kinetic energy of electron to excite a spectral line
of wavelength is given by
10
9 34
min
10 2536
) 10 998 . 2 )( 10 626 . 6 (
.) . (

= =
hc
E K
eV or J 890 . 4 10 833 . 7
19
=


4-4 ANGULAR MOMENTUM
Example 4-33
Calculate the value of Bohr magneton.
Solution
The Bohr magneton is defined as

e e
B
m
e
or
m
eh
2 4
h
=
1 24
31
34 19
10 273 . 9
) 10 109 . 9 ( 4
) 10 626 . 6 )( 10 602 . 1 (

= T J
B

The accepted value of Bohr magneton is
1 24
10 274 . 9

T J or
. 10 778 . 5
1 5
T eV
Example 4-34
Calculate the magnitude of the orbital angular momentum
of an electron in a state with 4 = l .
Solution
The magnitude of orbital angular momentum is given by
s J L
34 34
10 718 . 4 ) 10 055 . 1 ( ) 1 4 ( 4 ) 1 (

= + = + = h l l
Example 4-35
Write down the quantum numbers for all the hydrogen
atom states belonging to subshells for which 4 = n and 3 = l .
Solution
Now 4 = n and 3 = l . As
l
l
= .. ,......... 2 , 1 , 0 m
therefore the desired magnetic quantum numbers are
3 , 2 , 1 , 0 , 1 , 2 , 3 =
l
m
The spin quantum number is given by
2
1
=
S
m .

Example 4-36
A hydrogen state is known to have the quantum
number 3 = l . What are possible n,
l
m and
S
m .
Solution
The principal quantum number n must be greater than l
which is 3 for present case. Hence n = 4 and the magnetic
quantum number
l
m value are as under
3 , 2 , 1 , 0 , 1 , 2 , 3 =
l
m
The spin quantum number is given by
2
1
=
S
m .
Example 4-37
If an electron in a hydrogen atom is in a state with 5 = l ,
what is the smallest possible angle between L and
Z
L .
Solution
The minimum angle occurs when l
l
= m and is given by
[ ]
) 1 (
) 1 (
cos
min
+
=
+
= =
l l
l
h l l
h l
L
L
Z

[ ] 91287 . 0
) 1 5 ( 5
5
cos
min
=
+
=
2 4 5 24 1 . 24
0 0
min
= or

Example 4-38
Calculate and tabulate for a hydrogen atom in a state 3 = l ,
the allowed values of
Z
L ,
Z
and . Find the magnitude of L
and .
Solution
The corresponding values of magnetic quantum number
l
m for
3 = l are 3 , 2 , 1 , 0 , 1 , 2 , 3 =
l
m .The desired values are
calculated and tabulated below. Here we have employed the
following values
s J
34
10 055 . 1

= h and T J
B
/ 10 274 . 9
24
=
l
m
s m kg
m L
Z
/
2
h
l
=

T J
m
B Z
/

l
=

(
(
+
=

) 1 (
cos
1
l l
l
m

-3
34
10 165 . 3

23
10 782 . 2

0
0 . 150
-2
34
10 110 . 2

23
10 855 . 1

0
3 . 125
-1
34
10 055 . 1

24
10 274 . 9

0
8 . 106
0 0 0
0
0 . 90
1
34
10 055 . 1

24
10 274 . 9

0
2 . 73
2
34
10 110 . 2

23
10 855 . 1

0
7 . 54
3
34
10 165 . 3

23
10 782 . 2

0
0 . 30
The magnitude of orbital angular momentum is given by
s J L
34 34
10 655 . 3 ) 10 055 . 1 ( ) 1 3 ( 3 ) 1 (

= + = + = h l l
The magnitude of dipole moment is given by
T J
B
/ 10 213 . 3 ) ) 1 3 ( 3 )( 10 274 . 9 ( ) 1 (
23 24
= + = + =

l l


4-5 THE ZEEMAN EFFECT
Example 4-39
A hydrogen atom gas is placed in intense magnetic field of
0.8 tesla. Compute the separation between two consecutive
states (Normal Zeeman Effect) when = 5000 .
Solution
The wavelength separation is given by

hc
B
c m
eB
B
e
2 2
4

= = where
e e
B
m
e
or
m
eh
2 4
h
=

) 10 998 . 2 )( 10 626 . 6 (
) 10 5000 )( 8 . 0 )( 10 274 . 9 (
8 34
2 10 24

=

0937 . 0 10 337 . 9
12
or m
=

Example 4-40
What will be the separation, in , due to normal Zeeman
splitting of 4916 line in the mercury spectrum in a
magnetic field of 0.5 tesla?
Solution
) 10 998 . 2 )( 10 626 . 6 (
) 10 4916 )( 5 . 0 )( 10 274 . 9 (
8 34
10 24 2

= =

hc
B
B

2 12
10 64 . 5 10 64 . 5

= = m

Example 4-41
Calculate the wavelengths of the normal Zeeman Effect
triplet of a spectral line 5500 placed in a magnetic field of
10 tesla.
Solution
) 10 998 . 2 )( 10 626 . 6 (
) 10 5500 )( 10 )( 10 274 . 9 (
8 34
2 10 24 2

= =

hc
B
B

412 . 1 10 412 . 1
10
= =

m
The wavelengths of Zeeman triplet are
588 . 5498 412 . 1 5500
1
= = =
5500
2
= =
412 . 5501 412 . 1 5500
3
= + = + =
Example 4-42
The Zeeman components of a 500 nm spectral line are
0.0116 nm apart when the magnetic field is 1.00 tesla. Find
the ratio of e/m of the electron from this data.
Solution

c m
eB
e
4
2
=
or
2
) ( 4

B
c
m
e
e
=
2 9
9 8
) 10 500 )( 1 (
) 10 0116 . 0 )( 10 998 . 2 ( 4

=

e
m
e

kg C
m
e
e
/ 10 733 . 1
11
=

Example 4-43
A spectral line having a wavelength of 5500 shows a
normal Zeeman splitting of
2
10 1 . 1

. What is the
magnitude of the magnetic field causing the splitting?
Solution
hc
B
B
2

=
or
2 10 24
10 2 8 34
2
) 10 5500 )( 10 274 . 9 (
)} 10 )( 10 1 . 1 ){( 10 998 . 2 )( 10 626 . 6 ( ) (

=
B
hc
B
tesla B 078 . 0 =
Example 4-44
Find the minimum magnetic field needed for the Zeeman
Effect to be observed in a spectral line of 400 nm wavelength
when a spectrometer whose resolution is 0.010 nm is used.
Solution

hc
B
B
2

=
or
2
) (

B
hc
B

=
2 9 24
9 8 34
) 10 400 )( 10 274 . 9 (
)} 10 010 . 0 ){( 10 998 . 2 )( 10 626 . 6 (

= B
tesla B 339 . 1 =


CONCEPTUAL QUESTIONS
(1) What is meant by a stationary orbit in Bohrs theory of
Hydrogen atom?
Answer: - A stationary or allowed orbit is one in which electron
does not radiate any energy i.e. the total energy of the electron
remains constant.
(2) What should be the angular momentum of the electron
moving in an allowed orbit?
Answer: - The angular momentum of an electron should be an
integral multiple of ) 2 / ( h = h while moving in an allowed
orbit i.e. h n L = .
(3) How many electronic orbits are there in a Hydrogen
atom?
Answer: - Theoretically there are an infinite number of orbits in
a Hydrogen atom. As there is only one electron in the Hydrogen
atom, therefore one of these orbits will be occupied at one time.
The remaining orbits will be vacant.
(4) How is the spacing of adjacent electronic energy levels of
an atom affected by the value of n?
Answer: - The spacing of adjacent electronic energy levels of
an atom decreases as n increases.
(5) What is indicated by the existence of sharp lines in the
spectrum of Hydrogen atom?
Answer: - It indicates that the electron is moving in a given
orbit with certain frequency only.
OR
It indicates the presence of discrete energy levels in the
Hydrogen atom.
(6) Which transition of the electron in Hydrogen atom will
emit highest energy photon?
Answer: - The transition of the electron from = n to
1 = n will emit maximum energy photon. The energy of this
photon is eV eV E E 6 . 13 ) 6 . 13 ( ) 0 (
1
= =
.

(7) The total energy of the electron in Hydrogen atom is
negative. What is the physical significance of negative sign?
Answer: - It reflects the fact that the electron is bound to the
nucleus. An energy of 13.6 eV is needed to separate the electron
from the nucleus of hydrogen atom.
(8) Can a Hydrogen atom absorb a photon whose energy
exceeds its biding energy?
Answer: - Yes. The excess energy will appear as kinetic energy
of the detached electron of Hydrogen atom.
(9) Which series in the emission spectrum of Hydrogen atom
has the highest frequencies? In what part of the spectrum
are these lines?
Answer: - Lyman series. The spectral lines of Lyman series are
in the ultraviolet region.
(10) Any series of atomic Hydrogen yet to be discovered
will probably found to be in what region of the spectrum?
Answer: - In infrared region of the spectrum.
(11) If an electron moves to a larger orbit, does its total
energy increase or decrease? Does its kinetic energy
increase or decrease?
Answer: - The total energy of an orbiting electron is given by
r
e Z k
E
2
2
=
As r increases E becomes less negative and therefore increases.
The orbital kinetic energy of the electron is given by
r
e Z k
K
2
2
=
It is clear that K decreases with increase in r.
(12) Under what conditions an electron moving in the orbit
will have de Broglie wavelength?
Answer: -The electron orbit (i.e. the circumference of circular
orbit) must contain an integral number of de Broglie
wavelengths.

(13) What are two essential features of the vector atom
model?
Answer: - (a) Space quantization and (b) Hypothesis of
spinning electron.
(14) What is minimum energy needed to create an Electron -
positron pair?
Answer: - The minimum energy needed to create an electron-
positron pair is given by MeV c m 022 . 1 2
2
0
= .
(15) What is the wavelength of the photon corresponding to
the threshold energy needed to produce electron-positron
pair i.e. 1.022 MeV?
Answer: - 0.012


ADDITIONAL PROBLEMS
(1) Compute the first three wavelengths of the Bracket
series of hydrogen.
(2) The binding energy of electron in a certain state of
hydrogen atom is 0.85 eV. What is the corresponding
quantum number?
(3) A photon of energy 12.1 eV absorbed by a hydrogen
atom, originally in the ground state, raises the atom
to an excited state. What is the quantum number of
this state?
(4) Determine the speed of electron in the n = 8 orbit of
hydrogen atom. Use this value to find the
corresponding de Broglie wavelength.
(5) The lifetime of an excited state is about
8
10
second.
Compute how many revolutions an electron of
hydrogen atom in the excited state n = 4 will make
before jumping in the ground state?
(6) Which of the spectral lines of the Bracket series is
closest in wavelength to the first spectral line of the
Paschen series of hydrogen atom? What is difference
in their wavelengths?
(7) Find the radius of the smallest Bohr orbit in doubly
ionized lithium (
+ +
Li ). What will be the energy of
electron in this orbit?

Answers
(1) m and m m
6 6 6
10 166 . 2 10 625 . 2 , 10 051 . 4

(2) 4 (3) 3 (4)
1 5
10 734 . 2

s m , 2661
(5)
7
10 04 . 1 Revolutions (6) Fifth line (n = 9)
(7) 0.18 , -122 eV

Chapter 4 Atomic Structure (PP 96-125)

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CHAPTER 04 ATOMIC STRUCTURE 96

second, before it makes a downward transition and

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