Lecture 18

Motion of the Nucleus

C.M.
R
r
0

Center of mass:
0
0
0 0
r
M
m
R r m MR = ! =
Newtons law:
2
0
2
0
0
0
2
0
2
0
2
0
2
0
2
0
) (
4
1
) (
) (
4
1
r R
e
r R
M m
M
m
r R
e
R M r m
+
= +
+
+
= =
!"
#
!"
# #
Lecture 18
Reduced Mass
Therefore, we have
0
0
0
2
2
0
2
,
4
1
r R r and
M m
M m
where
r
e
r
+ =
+
=
=

!"
#
The effects of finite mass of the nucleus can be corrected
simply by replacing the mass of the electron by the reduced
mass .
Lecture 18
Effective Rydberg Constant
R =
m
0
e
4
8!
0
2
h
3
c
=
e
4
8!
0
2
h
3
c
M + m
0
M
We know
We get
R
M
!
e
4
8"
0
2
h
3
c
= R
1
1 + m
0
/ M
For example,
R
H
= R
1
1 + m
0
/ M
H
= 109677.584 cm
!1
R
D
= R
1
1 + m
0
/ M
D
= 109707.419 cm
!1
Lecture 18
Energy Level Diagram
2
6 . 13
n
eV
E
n
! =
Energy levels of the
hydrogen atom:
Ground state: n=1
eV E 6 . 13
1
! =
Excited states: n>1
Lecture 18
Transitions
Transitions from higher energy levels to lower energy
levels produce emission lines. For instance, the Lyman
series of the H atom originate in transitions from excited
states to the ground state.
Transitions from lower energy levels to higher energy
levels produce absorption lines. In extreme cases, an
electron in the ground state can absorb sufficient energy
to become a free electron. The minimum energy
required for such a process is referred to as the
ionization energy.
An electron can make a transition from one energy level to the
other:
Lecture 18
Excitation Mechanisms
Photo-excitation: an atom in the ground state absorbs a
photon (of energy less than the ionization energy) from the
radiation field to make a transition to an excited state.
Collisional excitation: an atom in the ground state acquires
energy (which is less than the ionization energy), in the
process of colliding with other energetic particles, to make
a transition to an excited state.
Lecture 18
Photoionization
Lyman series of the H atom correspond to transitions from
n>1 to the ground state n=1.
What is the inverse process?
Photo-excitation:
*
, 1
A hv A
n
! +
As n increases, the spacing between adjacent energy levels
decreases, and the energy of the n
th
level approaches that of
ionization. Therefore, it is possible for an electron in the
ground state to absorb a photon of energy greater than the
ionization energy to leave the atom. This process is known
as photoionization.
Lecture 18
Lyman Limit
There is a lower limit to the wavelength of photons associated
with each line series, arising fundamentally from the upper
limit to the energies of quantized states of an atom. The limit
is sometimes referred to as the series limit.
For example, for the Lyman series of the H atom, the limit
(commonly known as the Lyman limit) is given by
!
"
#
$
%
&
' =
2 2
1 1 1
m n
hc
E
I
(
1 = n
! = m hc
E
I
Ly
=
!
1
Lecture 18
Radiative Recombination
Recombination and Radiative Cascade:
! + + + ! +
" +
2 1
hv hv A e A
If an electron absorbs a photon of energy photon is greater
than E
I
, the electron will escape the atom with excess kinetic
energy. Photoionization can be symbolically expressed as
! +
+ " + e A hv A
What is the inverse process?
For instance, a proton collides with an free electron to
form an H atom, emitting photons in the process.
Lecture 18
Collisional Excitation
An atom (A) can also be ionized or excited by acquiring
energy in a collision with another particle (B):
B A B A
!
+ " +
*
or
B e A B A
!
+ + " +
# +
It is through this process that Frank and Hertz revealed the
first experimental evidence for the existence of discrete
energy levels in atoms.
Lecture 18
Demonstration of Ionization
Only when the electrons
have a certain minimum
energy eV
i
does the
current appear. The
corresponding voltage
V
i
is the ionization
potential of the atoms,
i.e., eV
i
= E
I .
Lecture 18
Franck-Hertz Experiment
The space between the grid and
anode A is filled with Hg vapor.
A braking voltage V
B
=0.5 V is
applied between the grid and A.
As soon as the voltage V
G

between the cathode and the
grid exceeds V
B ,
the current
increases but drops suddenly at
the integer multiples of about
5 V.

An intense emission line at
2537 A is observed, which
corresponds to a photon energy
of 4.85 eV.
Lecture 18
Physical Explanation
The energies of the electron in the Hg
atoms are quantized.
The discrete grid voltages at which the
current shows sudden drops corresponds
to the difference in the potential energy
between the ground state and an excited
state.
When the excited atoms return to the
ground state, they emit photons of
the same energy.
Improvement in the experimental technique led to the discovery
of more closely spaced structures, corresponding to energy levels.
Lecture 18
Photo-excitation vs. Collisional Excitation
As an example, sodium vapor at low pressure can be excited to
fluorescence by illumination with the yellow Na line (of which
the photons have an energy 2.11 eV). The excitation occurs
only when the light used has exactly the quantum energy 2.11
eV. Both smaller or larger quantum energies are ineffective
in producing an excitation.
On the other hand, sodium vapor can be excited by collisions
with electrons. In this case, the yellow line is emitted whenever
the energy of the electrons is equal to or greater than 2.11 eV.
The difference is a fundamental one. It is due to the fact that
the energy of photons is quantized but that of free electrons
is not.