Lecture 10 : Title : ALKALI SPECTRA

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In the previous lecture we have learnt the quantum mechanical treatment of hydrogen
atom.

The similar picture is not able to explain the alkali atoms, the other elements in the first
group of periodic table.

Here, we will discuss the development of the theory to explain the alkali spectra.

We will also elaborate the concept behind the modification of the potential required to
explain the observation in alkali atoms.
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The absorption spectra of alkali vapors (Such as lithium, sodium) appear quite similar in
many respects to the absorption spectrum of H atom. They are only displaced to a
considerable extent, toward longer wavelengths. These spectra also consist of a series of
lines with regularly decreasing separation and decreasing intensity.

⇒ It cannot, however, be represented by a formula completely analogous to the Bohr

formula. On the other hand, since the lines converge to a limit, we must be able to
represent them as differences between two terms.
Rydberg formula,
R
ν= TPS − where m = 2,3
(m + p)
2

p is a constant, known as Quantum Defect. TPS is known as series limit. This series is
known as Principal series.
⇒ Other series, in addition to this, may be observed for the alkalis. They are diffuse,
sharp and Bergmann series.
R
Sharp Series ν= TSS − m= 2,3
(m + s)
2

R
Diffuse Series ν=
TSS − m=
3, 4
(m + d )
2

R
Bergmann Series ν=
TBS − m=
4,5
(m + f )
2

∆n =0,1, 2,3
Selection rules:
∆ =±1
As an example, sodium energy levels and transitions are given in figure-10.1

Bergmann series

Sharp series Diffuse series

Principal series

Figure-10.1
Sodium atom energy levels and transitions
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As a specific example, we consider the alkali metals such as lithium, sodium and
potassium, which come from group I of the periodic table. They have one valence
electron outside filled inner shells. They are therefore approximately one-electron
systems, and can be understood by introducing a phenomenological number called the
quantum defect to describe the energies.

Let us consider the sodium atom. The optical spectra are determined by excitations of the
outermost 3s electron. The energy of each (n; l) term of the valence electron is given
by:

R
En ,l = − ……….10.1
(n − δ (l )) 2
Where n ≥ 3, δ (l ) is the quantum defect.

Nucleus +11e
3s

1s
2s

valence electron 2p

Sodium Atom Z = 11
Figure-10.2

The quantum defect δ (l ) was introduced empirically to account for the optical spectra. In
principle it should depend on both n and l, but it was found experimentally to depend
mainly on l as given in the following table.

Values of quantum defect for sodium

l n=3 n=4 n=5 n=6

0 1.373 1.357 1.352 1.349
1 0.883 0.867 0.862 0.859
2 0.010 0.011 0.013 0.011
3 0.000 -0.001 -0.008
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The dependence of the quantum defect on l can be understood with reference to the figure
where the radial probability densities for the 3s and 3p orbitals of a hydrogenic atom with
Z = 1 are plotted with respect to normalized radial distance.

An individual electron in sodium atom experiences an electrostatic potential due to the

Coulomb repulsion from all the other electrons in the atom. Ten out of eleven electrons
are in closed sub-shells, which have spherically-symmetric charge clouds. The off-radial
forces from electrons in these closed shells cancel because of the spherical symmetry.

Hydrogen radial probability distribution (figure-10.3) is expected to be a reasonable

approximation for the single valence electron of sodium.

⇒ We see that both the 3s and 3p orbitals 0.6

penetrate the inner shells, and that this 0.5 1s

penetration is much greater for the 3s 2s
Probability density

0.4
electron. 3s
0.3

⇒ The electron will therefore see a larger 0.2

effective nuclear charge for part of its orbit,


0.1
and this will have the effect of reducing the 0.0
0 5 10 15 20 25 30 35
energies. normalized radial distance r a0

⇒The energy reduction is largest for the 3s Radial Probability densities

electron due to its larger core penetration. 0.12
3S
0.10 3P
radial probability density

3D
0.08

0.06

0.04


0.02

0.00
0 5 10 15 20 25 30 35
normalized radial distance r a0

Figure-10.3
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The effect of this penetration results in the shift of energy levels. A comparison with the
hydrogen energy level is shown in figure-10.4.

Hydrogen energy levels Sodium energy levels

Figure-10.4

We can draw the conclusions that,

⇒ Energy levels with different  have different energies. In other words  degeneracy
removed.

⇒ From the hydrogen atom energy levels, it cannot be described, because energy
depends on “ n ” only.
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Classical Explanation
Penetrating and Non-Penetrating Orbits as shown in figure-10.5:
1) Non-Penetrating orbits
The first is the case when the outer electron has a non penetrating orbit, as in the
figure. If its accepted that the mean
symmetry of the cloud formed by ( Z − 1)
-e
electrons is similar, the electron experiences
the electrostatic potential of the nuclear
charge of Ze and of the spherical
distribution of charge ( Z − 1) . The
discussion presented for the hydrogen atom
remains valid. (Z-1)e

2) Penetrating orbit
On the other hand, if the orbit of the outer electron penetrates inside the core of
the atom, the problem is much more complex, simple solution by Somerfield, is
this,
1 e
Vext = " r " Large -e
4πε 0 r
1 Ze
=Vin + Const. " r " Small
4πε 0 r

(Z-1)e

Figure-10.5
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Quantum Mechanical Calculation

1 e2  b 
Form of the potential energy, V ( r ) =
− 1 +  …………….10.2
4πε 0 r  r 
This form represents the potential energy requirement at large distance,
1 e2
V (r ) = −
4πε 0 r
1 Z e2
and at small distance, V ( r ) = −
4πε 0 r
This potential with respect to radial distance is shown in figure-10.6

1 e2  b 
− 1 + 
4πε 0 r  r 

0
1 e2
−
4πε 0 r
2
 Potential V r

4
1 Ze 2
−
6 4πε 0 r

10
0 1 2

3
Radial distance r
4 5

Figure-10.6
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Since this is radial dependence and we need to solve only radial equation of the
Schrödinger equation of hydrogen atom problem
1 e2  b 
V (r ) =
− 1 + 
4πε 0 r  r 
c b 1 2
= 1 +  where, c =
− e
r r 4πε 0
Now, the Hamiltonian for one electron atom,
2 2
H =− ∇ +V (r )
2µ
2 2 c  b 
=− ∇ + 1 + 
2µ r r
2 2 c b
⇒− ∇ ψ + 1 + ψ = Eψ
2µ r r
2µ  c  b 
⇒ ∇ 2ψ + 2 
E −  1 +  ψ = 0
  r  r  ………..10.3

The radial equation:

d 2 χ  2µ 2 µ c  b   (  + 1) 
+  2 E − 2 1 +  −  R(r ) =0
dr 2
   r  r  r 2

d χ  2µ
2
2 µ c 2 µ c b  (  + 1) 
⇒ 2 − − 2 E + 2 + 2 2 +  R(r ) =0
d r  r  r r2 
…………10.4

2µ E 2µ c
Taking A =
− 2 ; B=
− 2 and substituting in equation 10.4
 

d 2χ  B − B b +  (  + 1) 
2
− A− + χ =
0
dr  r r2 
Let , * ( * + 1) =− B b +  (  + 1)

d 2χ  B − B b +  (  + 1) 
* *

So, −  A − + χ =
0
dr 2  r r2 

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Same radial equation as in hydrogen atom, solution with n* where n* = * + p + 1
R R
E=
− =
−
( n* ) ( * + p + 1)
2 2

n = + p + 1
So, n* = * + p + 1 = * −  + n
⇒ n* = n − (  − * ) = n − ∆

Now,
* ( * + 1) =  (  + 1) − B b

( )
⇒  2 − ( * ) + (  − * ) =
2
Bb

⇒ (  − * )(  + * + 1) =
Bb
Bb Bb
=
⇒ ∆ =
 +  + 1 2 + 1
*

B b
2 b 1
= =
+ 1 a1  + 1
2 2
Rhc
En , = − 2
 b 1 
n− 
 a1  + 1 
 2

Note that :
This energy expression is dependent on both n and l

Maximum l -> small correction

Small l -> correction term is large
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Rhc
En,  = − 2
 Bb 
n − 
 2 + 1 

Now we know
E = hν
c 1
=ν = ν
λ λ
hc
E = ⇒ cm −1 =
λ
1
λ
( E
hc
)
R
En,  = − 2
cm −1
 Bb 
n − 
 2 + 1 
Where R = 109, 728.7 cm −1

Conversion
ergs / molecule Cal / molecule electron volts
1 cm −1 1.9858 ×10−16 2.8575 1.23954 ×10−4

Take an example:
Lithium : ionization potential : 43, 486 cm −1 or, 5.39 eV
109728.7
43486 =
( 2 − B b )2
⇒ (2 − B b) =
2
2.5233
⇒ 2− Bb = 1.588
⇒ Bb = 0.41
109728.7
=E2,1 = 2
31603.8 cm −1
 0.41 
2− 
 2 
109728.7
=E3,0 = 16357.6 cm −1
( 3 − 0.41) 2

109728.7
=E3,1 = 2
13383.7 cm −1
 0.41 
3− 
 3 
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109728.7
=E4,0 = 8513.9 cm −1
( 4 − 0.41) 2

109728.7
=E4,1 = 2
7351.8 cm −1
 0.41 
4− 
 3 
109728.7
=E4,2 = 2
7148.1 cm −1
 0.41 
4− 
 5 

109728.7
=E4,3 = 2
7063.4 cm −1
 0.41 
4− 
 7 

l=0 l=1 l=2 l=3

5000 cm-1
4f
-1 4p 4p
10000 cm 4s

15000 cm-1 3p 3d
3s
20000 cm-1

25000 cm-1

30000 cm-1 2p

35000 cm-1

40000 cm-1
2s
-1
45000 cm

Figure-10.7
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Recap

In this lecture, we have learnt that

⇒ The departure in the spectra of alkali atom from hydrogen such as lithium, sodium is
that the energies are not only dependent on n but also l.

⇒ The modification of the potential of electron in such multielectronic atoms is that the
energy correction term is large of small l values.