CHEM 352: Examples for chapter 2.

1. The quantum mechanical state of a hydrogen atom is described by the

following superposition:
1
ψ = √ (2ψ1,0,0 − 3ψ2,0,0 − ψ3,2,2 )
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where ψn,l,m are eigenfunctions of the Hamiltonian. The subscripts
refer to quantum numbers n, l, m.

(a) What is the probability of finding the hydrogen atom in states

(n = 1, l = 0, m = 0), (n = 2, l = 0, m = 0), (n = 3, l = 2, m = 2)
or in some other state?
~
(b) What are the expectation values for energy, L̂2 and L̂z ?

Solution:

First we check that the wavefunctions are normalized. For hydro-

genlike atom orbitals we have the following orthonormality condition:
hψn,l,m |ψn′ ,l′ ,m′ i = δnn′ δll′ δmm′ . The normalization of the given wave-
function can now be evaluated:
1
hψ |ψ i = h2ψ1,0,0 − 3ψ2,0,0 − ψ3,2,2 |2ψ1,0,0 − 3ψ2,0,0 − ψ3,2,2 i
14
1
= (4 + 9 + 1) = 1 (due to orthonormality)
14
(a) The probabilities for the energy eigenstates are given by squaring
their coefficients in the wavefunction. The probabilities are then:
P (1, 0, 0) = 4/14 = 2/7, P (2, 0, 0) = 9/14 and P (3, 2, 2) = 1/14.
(b) The expectation value for energy is:
D   E 1 D   E
   
ψ Ĥ  ψ = 2ψ1,0,0 − 3ψ2,0,0 − ψ3,2,2 Ĥ  2ψ1,0,0 − 3ψ2,0,0 − ψ3,2,2
 14 
=E1,0,0 =E2,0,0 =E3,2,2
z
D }| E{ z
D }| E{ zD }| E{
1       
= 4 ψ1,0,0 Ĥ  ψ1,0,0 +9 ψ2,0,0 Ĥ  ψ2,0,0 + ψ3,2,2 Ĥ  ψ3,2,2 
14  

2 9 1
= E1,0,0 + E2,0,0 + E3,2,2
7 14 14
1
 The numerical values for En,l,m ’s can be calculated from:
hcR −13.6 eV E1
En = − 2
= 2
= 2
n n n
D E
Thus the numerical value for Ĥ is:
D E 2 9 1 1 1

229
Ĥ = + × + × E1 = E1 ≈ −6.2 eV
7 14 4 14 9 504

~
The expectation value for L̂2 is:
~
L̂2 |ψn,l,m i = l(l + 1)h̄2 |ψn,l,m i
D E h̄2 3
~
L̂2 = (0 + 0 + 2(2 + 1))) = h̄2
14 7

The expectation value for L̂z is:

L̂z |ψn,l,m i = mh̄ |ψn,l,m i

D E h̄ 1
L̂z = (0 + 0 + 2) = h̄
14 7

~
2. Show that operators L̂z and L̂2 = L̂2x + L̂2y + L̂2z commute with the
hydrogen atom Hamiltonian operator:
   
h̄2 h̄2 ~2
− ∆ + V̂ , L̂z = − ∆ + V̂ , L̂ = 0
2m 2m

where V̂ is the operator corresponding to electron - nuclear Coulomb

interaction. Use spherical coordinates and remember that operators
commute, for example, if they depend on different variables. What is
the significance of this result?
Solution:

The Hamiltonian consists of the kinetic energy part, which is propor-

tional to the Laplacian operator, and the Coulomb potential. Laplacian
in spherical coordinates is (see lecture notes or a tablebook):

2
    
1 ∂
2 2 ∂ 1 ∂ ∂ 1 ∂2
∆≡∇ = 2 r + 2 sin(θ) +
r ∂r ∂r r sin(θ) ∂θ ∂θ r2 sin2 (θ) ∂φ2

The Coulomb potential depends on only on spatial coordinate r (e.g.

the distance between the nucleus and the electron). Tje L̂z operator is
defined in spherical coordinates as:

∂
L̂z = −ih̄
∂φ
This clearly commutes with the first two terms in the Laplacian because
those terms do not depend on φ. The third depends on φ but both
operators consisth of differentiation
i with respect to φ and hence they
commute. Thus Ĥ, L̂z = 0.
~
Next we consider L̂2 . This is operator can be written in spherical
coordinates as:
   
~2 2 1 ∂ ∂ 1 ∂2
L̂ = −h̄ sin(θ) +
sin(θ) ∂θ ∂θ sin2 (θ) ∂φ2
This does not depend on r and therefore it commutes with the Coulomb
potential and the first term in the Laplacian, which depends only on
~
r. Apart from r and some constants L̂2 is identical to the angular part
of
h the iLaplacian. Operators always commute with themselves. Thus
~
Ĥ, L̂2 . The significance of these results is that both the energy and
the quantum numbers l and ml can be specified simultaneously.

3. Demonstrate that the Cartesian hydrogen like px and py orbitals are

not eigenfunctions of L̂z but their linear combinations px ± ipy are.
Solution:

It is convenient to express the Cartesian orbitals in spherical coordi-

nates (see lecture notes):
px = sin(θ) cos(φ)f (r) where f (r) contains all r dependency
py = sin(θ) sin(φ)f (r)

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 To simplify calculations, the φ containing part is rewritten as:

1 iφ
1 iφ

cos(φ) = e + e−iφ and sin(φ) = e − e−iφ
2 2i
The L̂z operator in spherical coordinates was already given in the pre-
vious problem. Next we operate on px and py by L̂z :

sin(θ) d iφ
1 iφ

L̂z px = −ih̄f (r) e + e−iφ = ih̄ f (r) sin(θ) × e − e−iφ = ih̄py
2 dφ | 2i
{z }
=py

Thus the operation does not yield a constant times the original function
(e.g. not an eigenfunction). In similar way we can show that py is not
an eigenfunction of L̂z : L̂z py = −ih̄px .
Next we show that the following linear combinations are eigenfunctions
of L̂z :
  
f (r) sin(θ) iφ 1 iφ 1 −iφ
px + ipy = e +e +i
−iφ
e − e = f (r) sin(θ)eiφ
2 i i
px − ipy = f (r) sin(θ)e−iφ

When operating on these by L̂z we get:

L̂z (px + ipy ) = h̄ f (r) sin(θ)eiφ = h̄(px + ipy )

| {z }
=px +ipy

L̂z (px − ipy ) = −h̄f (r) sin(θ)eiφ = −h̄(px − ipy )

These have the right form (e.g. constant × the original function) and
therefore they are eigenfunctions of L̂z .

4. (a) Consider a hydrogenlike atom with on electron on 2s orbital.

What is the most probable distance from the nucleus? Use the
radial wavefunction in your calculation.

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(b) Show that the following hydrogenlike atom orbital pairs are or-
thogonal: (1s, 2s) and (2px , 2py ).
Solution:

(a) The radial part for 2s orbital is (with ρ = 2Zr/a0 substituted in):
 3/2  
1 Z Zr − 2aZr
R2,0 = √ 2− e 0
2 2 a0 a0

The corresponding radial probability density is:

 3  2
2 2 2 2 2 1 Z Zr − Zr
P2,0 (r) = r N2,0 R2,0 = N2,0 r × 2− e a0
8 a0 a0

Next we must find the maximum value for P2,0 (r). To do this, we
look for zeros of the first derivative (with respect to r):

dP2,0 (r) rZ 3

= 6 e−Zr/a0 8a30 − 16a20 rZ + 8a0 r2 Z 2 − r3 Z 3 = 0
dr 8a0

The four
√ roots

for this equation are: r = 0, r = 2a0 /Z and r =
a0
Z
3 ± 5 . Next we have to check which root gives the highest
probability:

P2,0 (0) = 0
P2,0 (2a0 /Z) = 0
a 
0
√  2 2Z  √  √ Z
P2,0 3 + 5 /N2,0 = 9 + 4 5 e−(3+ 5) ≈ 0.191 ×
Z a0 a0
a 
0
√ 
2 2Z  √  √ Z
P2,0 3 − 5 /N2,0 = 9 − 4 5 e−(3− 5) ≈ 0.0519 ×
Z a0 a0
√

Thus the maximum is reached at r = aZ0 3 + 5 . One could
check the second derivatives the further characterize√this

as a max-
a0
ium. The most probable radius is therefore Z 3 + 5 ≈ 5.2× aZ0 .
Note that this is in agreement with the plot given in the lecture
notes.

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(b) First we show that 1s and 2s orbitals are orthogonal. The wave-
functions are (see lecture notes):
 3/2
1 Z
ψ1,0,0 =√ e−Zr/a0
π a0
 3/2  
1 Z Zr Zr
− 2a
ψ2,0,0 = √ 2− e 0
4 2π a0 a0

These functions depend only on r and therefore we just need to

integrate over r and may drop the constants:
Z∞   Z∞  
Zr Zr
− 2a 2 2 Zr3 − 3Zr
e −Zr/a0
× 2− e 0 r dr = 2r − e 2a
0 dr
a0 a0
0 0
Z∞ Z∞
− 3Zr Z − 3Zr
=2 r2 e 2a
0 dr − r3 e 2a 0 dr
a0
0 0
32a30 32a30
= − =0
27Z 3 27Z 3
where in the last step the integrals were looked up from a table-
book.
Next we show that 2px and 2py are orthogonal. An easy way to
see this is to note the angular dependencies of the orbitals:
1
px = − √ (p+1 − p−1 ) ∝ sin(θ) cos(φ)
2
i
py = √ (p+1 + p−1 ) ∝ sin(θ) sin(φ)
2

The only difference is in the φ part. The angular integral over φ

is:
Z2π
cos(φ) sin(φ)dφ = 0 (integrand is odd)
0

Because this angular part yields zero, integration over all spherical
variables gives also zero. Hence px and py are orthogonal to each
other.

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5. (a) Write the electron configuration for V2+ ion. What quantum num-
bers for the total electron spin are possible in this configuration?
(b) If two electrons reside on two different orbitals, what are the pos-
sible values for total spin and the multiplicity? What values are
possible for three electrons on different orbitals?
Solution:

(a) V (vanadium) has 23 electrons and therefore V2+ has 21 electrons.

From the lecture notes one can find the electron configuration as:
V (Ar3d3 4s2 ) and V2+ (Ar3d3 ). Two electrons can give either
S = 1 or S = 0. However, since we have three electrons we must
couple this to the third electron: S = 3/2, 1/2 or S = 1/2. This
the possible values for S are 3/2 and 1/2.
(b) Two electrons on different orbitals: s1 = 1/2 and s2 = 1/2. This
can give S = 1 or S = 0. The multiplicity (2S + 1) can therefore
be either 3 (triplet) or 1 (singlet). Coupling a third electron to
this gives: S = 3/2, 1/2 or S = 1/2 (just in previously). The
multiplicity can now be either 4 (quartet) or 2 (doublet).

6. (a) What information do the following term symbols provide about a

given atom: 1 D2 and 3 F4 ?
(b) Consider the emission spectrum of potassium atom, which exhibits
lines at λ1 = 766.70 nm and λ2 = 770.11 nm. What is the value
of the spin-orbit coupling constant? The emission lines originate
from the 2 P excited state (spin-orbit split).
(c) Which of the following atomic transitions are (dipole) allowed:
5d → 2s, 5p → 3s, 5p → 3f ?
Solution:

(a) In 1 D2 state there are no unpaired electrons (singlet state) and

hence the total spin S = 0. The angular momentum quantum

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 number
D E L = 2, which means that the total angular momentum
~
L̂2 = 2(2 + 1)h̄2 = 6h̄2 . The total angular momentum quantum
number J = 2 (specified by the subscript). In 3 F4 state the mul-
tiplicity (2S + 1) is 3 which gives S = 1 (triplet state) and F term
implies L = 3. The total angular momentum quantum number is
specified as J = 4.
(b) The energy level diagram for alkai metal atoms is:

The two emission lines originate from the two 2 P states, which are
split by the spin-orbit interaction, and terminate to the ground
2
S state. Hence the energy difference between the two emission
lines gives the energy difference between the spin-orbit split states
2
P1/2 and 2 P3/2 . The line positions must be converted to energy
by relation E = hν = hc λ
(h is the Planck’s constant and c is the
speed of light). To calculate A, we have to calculate the energy
difference between 2 P1/2 and 2 P3/2 :

2 A
P1/2 : ESO = [J(J + 1) − L(L + 1) − S(S + 1)] = −A
2
2 A 1
P3/2 : ESO = [J(J + 1) − L(L + 1) − S(S + 1)] = A
2 2
3
∆ESO = A
2
Next we calculate the energies for the observed transitions. For
2
P3/2 →2 S1/2 we have:
2.9979 × 108 m/s
E1 = hν1 = hc/λ1 = (6.6261 × 10−34 Js) ×
766.70 × 10−9 m
= 2.5909 × 10−19 J = 1.6171 eV = 13043 cm−1

For 2 P1/2 →2 S1/2 :

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 2.9979 × 108 m/s
E2 = hν2 = hc/λ2 = (6.6261 × 10−34 Js) ×
770.11 × 10−9 m
= 2.5794 × 10−19 J = 1.6099 eV = 12985 cm−1

Thus the energy difference is ∆ESO = 39 cm−1 which gives A =

2∆ESO /3 = 39 cm−1 .
(c) The selection rule is ∆l = ±1. For 5d → 2s we have ∆l = −2
and hence it is forbidden. Transition 5p → 3s has ∆l = −1 and
therefore it is allowed. 5p → 3f has ∆l = +2 and it is forbidden.

7. (a) Write all the term symbols that can be obtained from the follow-
ing electron configurations: 2s1 2p1 , 2p1 3d1 and Ar4s2 3d10 4p5 (Br
atom).
(b) Write the term symbols for carbon atom (He2s2 2p2 ), which has
two equivalent p-electrons. Hint: tabulate all possible ml1 , ml2 , ms1
and ms2 values and calculate the total L and S values. Remember
to exculde the Pauli forbidden states.
Solution:

(a) Consider 2s1 2p1 electron configuration. The s-shell has l1 = 0

with s1 = 1/2 and p-shell has l2 = 1 and s2 = 1/2. The total L =
l1 + l2 , ..., |l1 − l2 | = 1. The total spin S = s1 + s2 , ..., |s1 − s2 | =
1, 0. Thus the total J = L + S, ..., |L − S| can be 2, 1 or 0 (for
L = 1, S = 1) or 1 (L = 1, S = 0). This results in the following
term symbols: 3 P2 ,3 P1 ,3 P0 and 1 P1 .
For 2p1 3d1 we can have the following:
p-electron: l1 = 1, s1 = 1/2.
d-electron: l2 = 2, s2 = 1/2.

Hence L = 3, 2, 1 and S = 1, 0. This gives the following total J

values:
• L = 3 and S = 1 results in J = 4, 3, 2 (3 F4 , 3 F3 and 3 F2 term
symbols)

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 • L = 3 and S = 0 results in J = 3 (1 F3 term symbol)
• L = 2 and S = 1 results in J = 3, 2, 1 (3 D3 , 3 D2 and 3 D1
term symbols)
• L = 2 and S = 0 results in J = 2 (1 D2 term symbol)
• L = 1 and S = 1 results in J = 2, 1, 0 (3 P2 , 3 P1 and 3 P0 term
symbols)
• L = 1 and S = 0 results in J = 1 (1 P1 term symbol)
For Ar4s2 3d10 4p5 we have only one unpaired electron which has
l = 1 and s = 1/2. This gives obviously L = 1 and S = 1/2 and
the total J = 3/2 or 1/2. Hence the two possible term symbols
are 2 P3/2 and 2 P1/2 .
(b) Carbon has 2 equivalent p-electrons: l1 = l2 = 1 and s1 = s2 =
1/2. We should tabulate all the possible states - including ML =
ml1 + ml2 and MS = ms1 + ms2 .

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