FAQs & their solutions for Module 6:

Hydrogen like atoms and other central potentials

Question1: In spectroscopy the energy levels are usually written in wave number units which
are obtained by dividing En by hc:

En Z2
Tn = =− R (1)
hc n2
Using the expression for En , show that the Rydberg constant R is given by

μ cα 2
R= (2)
2h
where
q2 1
α = ≈ (3)
4 πε 0 =c 137.036
h
represents the fine structure constant, = = = 1.05457266 × 10−34 Js and
2π
c = 2.9979258 × 108 m/s represents the speed of light in free space.

Solution 1: The energy eigen‐values for a hydrogen‐like atom is given by:

| E1 |
En = − (4)
n2
where

n = 1, 2, 3,….
represents the total quantum number and

1
| E1 | = μ Z 2α 2 c 2 (5)
2
represents the magnitude of the ground state energy. Thus we may write

En Z2
Tn = =− R
hc n2

where
 μ cα 2
R= (6)
2h

is known as the Rydberg’s constant.

Q uestion2: In continuation of the previous problem, calculate the values of the Rydberg
constant for the hydrogen atom, the deuterium atom and the singly ionized Helium atom
(which are all hydrogen like atoms).You may assume

me = 9.1093897 × 10-31 kg ; m p = 1.6726231× 10-27 kg ; mn = 1.6749286 × 10-27 kg ;

md = 3.3435860 × 10-27 kg and mα = 6.644656209 × 10-27 kg (7)

where me , m p , mn , md and mα represent the masses of the electron, proton, neutron,

deuteron and the alpha particle respectively.

Solution2: The reduced mass is given by

me mN
μ= (8)
me + mN

Using me = 9.1093897 × 10-31 kg ; m p = 1.6726231× 10-27 kg ; mn = 1.6749286 × 10-27 kg ;

md = 3.3435860 × 10-27 kg and mα = 6.644656209 ×10-27 kg we readily get

R = 109677.58 cm −1 (for the hydrogen atom)

109707.56 cm −1 (for the deuterium atom)
109722.40 cm −1 (for the He+ - atom)

The slight difference in the values is because of the difference in the values of the reduced mass
μ.

Q uestion3: Show that (for a hydrogen like atom) for the n = n1 → n = n2 transition, the
wavelength of the emitted radiation is given by
−1
2h ⎡1 1⎤
λ= 2 2 2 ⎢ 2
− 2⎥ (9)
μZ α c ⎣ n2 n1 ⎦
When n2 = 1, 2 and 3 we have what is known as Lyman series, the Balmer series and the
Paschen series respectively.

Solution3: For the n = n1 → n = n2 transition, the wavelength of the emitted radiation is

given by

hc
λ = (10)
En 1 − E n2

or
−1
⎡1
2h 1⎤
λ= 2 2 2 ⎢ 2
− 2⎥ (11)
μZ α c ⎣ n2 n1 ⎦

Q uestion4: In continuation of the previous problem, calculate the wavelength of the emitted
radiation for the n = 3 → n = 2 and for the n = 4 → n = 2 transitions in hydrogen and
deuterium.

Solution4: For the n = 3 → n = 2 transition, the wavelength of the emitted radiation is given
−1
2h ⎡1 1⎤
by λ = − . Using the data given in Problem 6.2, we can calculate the reduced
μ Z α c ⎣ 4 9 ⎥⎦
2 2 2 ⎢

mass to obtain the following values of the wavelength of the emitted radiation:
o o
6565.2 A and 6563.4 A in hydrogen and deuterium respectively. Similarly for the
n = 4 → n = 2 transition, the wavelength of the emitted radiation is given by
−1
2h ⎡1 1 ⎤
λ= − and using the data given in Problem 6.2, we can calculate the reduced
μ Z α c ⎣ 4 16 ⎥⎦
2 2 2 ⎢

mass to obtain the following values of the wavelength of the emitted radiation:
o o
4863.1 A and 4861.7 A in hydrogen and deuterium respectively.

Question5: Write the radial part of the Schrodinger equation for the hydrogen‐like atom
problem for which

Z q2
V (r ) = − (12)
4π ε 0 r
where
 Z=1 for the H‐atom problem,

Z=2 for the singly ionized He‐atom problem (He+),

Z=3 for the doubly ionized Li‐atom problem (Li++)

Define a new radial function

u (r ) = r R (r ) (13)
and also a new variable ρ = γ r and study the solutions of the radial part of the Schrodinger equation
as ρ → 0 and as ρ → ∞. Using these limiting behaviors, write the solution as

u ( ρ ) = ρ l +1 e − ρ / 2 y ( ρ ) (14)

and show that y ( ρ ) satisfies the confluent hypergeometric equation. Show that if the confluent
hypergeometric function is made into a polynomial, one obtains the energy eigenvalues of the problem.

Solution5: For the hydrogen‐like atom problem, the radial part of the Schrödinger equation is
given by

1 d ⎛ 2 dR ⎞ 2 μ ⎡ l (l + 1)= 2 ⎤
⎜ r ⎟ + ⎢ E − V ( r ) − ⎥ R(r ) = 0 (15)
r 2 dr ⎝ dr ⎠ = 2 ⎢⎣ 2μr 2 ⎥⎦

If we define a new radial function

u (r ) = r R(r ) (16)
we would get

dR d ⎡u ( r) ⎤
r2 = r2 ⎢ ⎥
dr dr ⎣ r ⎦
du
= r −u( r)
dr
Thus

1 d ⎛ 2 dR ⎞ 1 d 2 u
⎜r ⎟= (17)
r 2 dr ⎝ dr ⎠ r dr 2
and the radial part of the Schrödinger equation would become
 d 2u ( r ) 2 μ ⎡ Z q2 l (l + 1)= 2 ⎤
+ 2 ⎢ E + − ⎥ u (r ) = 0 (18)
dr 2 = ⎣ 4π ε 0 r 2μ r 2 ⎦

We introduce the variable ρ = γ r to obtain

d 2u ⎡ 1 λ l (l + 1) ⎤
+ ⎢− + − u(ρ ) = 0 (19)
dρ 2
⎣ 4 ρ ρ 2 ⎥⎦

8μ E
where γ 2 = − (20)
=2

2μ Z ⎛ q 2 ⎞ μ
and λ= ⎜ ⎟ = Zcα (21)
= 2γ ⎝ 4πε 0 ⎠ 2E

d 2u 1
As ρ → 0, Eq.(11) becomes − u ( ρ ) = 0 the well‐behaved solution of which is
dρ 2
4
d 2u l (l + 1)
u(ρ) = e −ρ / 2
. As ρ → ∞ , Eq.() becomes − u ( ρ ) = 0 the well‐behaved solution of
dρ2 ρ2
which is u ( ρ ) = ρ l +1 . This suggests we try out the solution u ( ρ ) = ρ l +1 e − ρ / 2 y ( ρ ) . Simple
manipulations would give

d2y dy
ρ + (c − ρ ) − a y(ρ ) = 0 (22)
dρ 2
dρ

which is the confluent hypergeometric equation. In the above equation

a = l +1− λ and c = 2l + 2 (23)

The well behaved solution of the above equation is

a a (a + 1) ρ 2
y(ρ ) = 1 F1 ( a , c, ρ ) = 1 + ρ + +" (24)
c c (c + 1) 2!
represents the confluent hypergeometric function. If the series is not terminated, then as ρ → ∞ , it
will behave as e ρ . Thus the series must be made into a polynomial and for that to happen we must
have

a = − nr ; where nr = 0,1, 2..... (25)

which is known as the radial quantum number. Thus λ = l + 1 + nr = n and we readily obtain
 μ Z 2α 2 c 2
En = − (26)
2n 2

Question6: For the hydrogen‐like atom problem, the radial part of the wave function is given
by:

Rnl ( ρ ) = N e − ρ / 2 ρ l 1 F1 (l + 1 − n, 2l + 2, ρ ) ; n = 1, 2, 3,...
(27)
l = 0,1, 2, ....n − 1
where

2Z ⎫
ρ = γr ; γ =
na0 ⎪⎪
=2 ⎬ (28)
a0 = ⎪
μ (q 2 / 4πε 0 ) ⎪⎭

is the Bohr radius. Further

a a (a + 1) ρ 2
1 F1 ( a, c, ρ ) = 1 + ρ + +" (29)
c c (c + 1) 2!
represents the confluent hypergeometric function and N represents the normalization
constant. Obtain the normalized functions R2 0 ( r ) , R2 1 ( r ) , R3 0 ( r ) , R3 1 ( r ) and R3 2 ( r ) .

Solution 6: The normalization condition is given by

∞

∫ R nl (r) 2
r 2 dr = 1 (30)
0

ρ
For n = 2, l = 0 we will have 1 F1 ( − 1, 2, ρ ) = 1 − . Thus the normalization condition becomes
2
∞
⎛ ρ⎞
2
N2
3 ∫
−ρ
e ⎜1 − ⎟ ρ 2 d ρ = 1
γ 0 ⎝ 2⎠

∞
N2 −ρ ⎛ 2 ρ4 ⎞
γ 3 ∫0
⇒ e ⎜ ρ − ρ 3
+ ⎟ dρ =1
⎝ 2 ⎠

Simple integrations will give

3/ 2
1 ⎛Z⎞
1/ 2
⎡ 2! ⎤ ⎜ ⎟
N =γ 3/2
⎢ 4 × 1⎥ = (31)
⎣ ⎦ 2 ⎜⎝ a0 ⎟⎠
Thus
 3/ 2
1 ⎛Z⎞ ⎛ 1 ⎞ −ξ / 2
R2 0 ( r ) = ⎜ ⎟ ⎜1 − ξ ⎟ e (32)
2 ⎝ a0 ⎠ ⎝ 2 ⎠

r
where ξ = . Similarly, one can calculate other wave functions:
a0

3/ 2
⎛Z ⎞
R1 0 ( r ) = 2 ⎜ ⎟ e −ξ (33)
⎝ a0 ⎠

3/ 2
1 ⎛Z⎞
R2 1 ( r ) = ⎜ ⎟ ξ e −ξ / 2
2 6 ⎝ a0 ⎠
3/ 2
2 ⎛Z⎞ ⎛ 2 2 2 ⎞ −ξ / 3
R3 0 (r )= ⎜ ⎟ ⎜1 − ξ + ξ ⎟ e
3 3 ⎝ a0 ⎠ ⎝ 3 27 ⎠
3/ 2
(34)
8 ⎛Z⎞ ⎛ 1 2 ⎞ −ξ / 3
R3 1 ( r ) = ⎜ ⎟ ⎜ξ − ξ ⎟ e
27 6 ⎝ a0 ⎠ ⎝ 6 ⎠
3/ 2
4 ⎛Z ⎞
R3 2 ( r ) = ⎜ ⎟ ξ 2 e −ξ / 3
81 30 ⎝ a0 ⎠

Question7: Write the radial part of the Schrodinger equation for the 3‐dimensional oscillator
problem for which

1
V (r ) = μ ω 2r 2 (35)
2
Define a new variable

μω
ξ = γ 2r 2 ; γ = (36)
=

and study the solutions of the radial part of the Schrodinger equation as ξ → 0 and as
ξ → ∞. Using these limiting behaviors, write the solution as

R ( ξ ) = ξ l / 2 e −ξ / 2 y ( ρ ) (37)

and show that y ( ρ ) satisfies the confluent hypergeometric equation. Show that if the
confluent hypergeometric function is made into a polynomial, one obtains the energy
eigenvalues of the problem.
Solution7: For the 3‐dimensional oscillator problem for which

1
V (r ) = μ ω 2 r 2 , the radial part of the Schrödinger equation is given by
2

1 d ⎛ 2 dR ⎞ 2 μ ⎡ 1 l (l + 1)= 2 ⎤
⎟+ ⎢E − μ ω r − ⎥ R(r ) = 0
2 2
⎜r (38)
r 2 dr ⎝ dr ⎠ = 2 ⎣ 2 2μ r 2 ⎦

We define a new variable

μω
ξ = γ 2r 2 ; γ = (39)
=

to obtain

d 2R 3 dR ⎡ E l (l + 1) 1 ⎤
+ + ⎢ − − ⎥ R(ξ ) = 0 (40)
dξ 2
2ξ d ξ ⎣ 2=ωξ 4ξ 2 4⎦

d 2R 1
As ξ → 0, the above equation becomes − R (ξ ) = 0 the well‐behaved solution of
dξ 2
4
which is R (ξ ) = e −ξ / 2 . As ξ → ∞ , the equation becomes

d 2R 3 dR l (l + 1)
+ − R(ξ ) = 0 (41)
dξ 2
2ξ dξ 4ξ 2

the well‐behaved solution of which is R (ξ ) = ξ l / 2 . This suggests we try out the

solution R (ξ ) = ξ l / 2 e −ξ / 2 y (ξ ) . Simple manipulations would give

d2y dy
ξ + (c − ξ ) − a y (ξ ) = 0 (42)
dξ 2
dξ

which is the confluent hypergeometric equation. In the above equation

 l 3 E 3
a= + − and c= l+ (43)
2 4 2=ω 2

Once again, the well behaved solution of the above equation is

a a (a + 1) ξ 2
y (ξ ) = F ( a , c , ξ ) = 1 + ξ + +" (44)
c (c + 1) 2!
1 1
c
which represents the confluent hyper geometric function. If the series is not terminated, then
as ξ → ∞ , it will behave as eξ . Thus the series must be made into a polynomial and for that to
happen we must have

a = − nr ; where nr = 0,1, 2..... (45)

Thus the eigen values of the problem are

⎛ 3⎞
E = ⎜ 2nr + l + ⎟ =ω (46)
⎝ 2⎠