Unit 1

Quantum Theory and Spectroscopy

1. State four postulates of quantum mechanics
2. State the three conditions that a wavefunction must fulfill to be suitable for utilisation in
quantum mechanics
3. Normalise the function  (x) = a(a-x) over the interval 0  x  a
 d2
4. Which of the following functions are eigenfunctions of the operator
dx 2
a)  (x) = e2x
b)  (x) = x2
c)  (x) = sin8x
d)  (x) = sin3x-cos3x
4. Solution
d 2x
a)  (x) = e 2x
First derivative e 2e 2 x 
dx

d
The second derivative is 2e 2 x 4e 2 x 
dx
Since the operation returns the original function multiplied by a
constant, a2, then e–2x is an eigenfunction of the operator d2/dx2
with eigenvalue 4. 
4. Solution
d 2
b)  (x) = x 2
First derivative x 2 x *½
dx

d
The second derivative is 2 x 2 *½
dx
Since the operation does not return the original function  (x) = x2
is not an eigenfunction of the operator d2/dx2 
4. Solution d
c)  (x) = sin8x First derivative sin 8 x 8 cos 8 x *½
dx
d
The second derivative is dx 8 cos 8 x  64 sin 8 x
*½

Since the operation returns the original function multiplied by a

constant, -64, then  (x) = sin8x is an eigenfunction of the operator
d2/dx2 with eigenvalue -64. 
4. Solution

d)  (x) = sin3x-cos3x

d
First derivative sin 3 x  cos 3 x 3 cos 3 x  3 sin x 
dx
d2 
The second derivative is 2
sin 3x  cos 3x   9 sin 3x  9 cos 3x
dx


d2
Which can be rearranged so that 2
sin 3x  cos 3x   9(sin 3x  cos 3x)
dx

Since the operation returns the original function multiplied by a

constant, -9, then  (x) = sin3x-cos3x is an eigenfunction of the
operator d2/dx2 with eigenvalue -9. 
5. Calculate the energy levels of the -network in octatetraene, C8H10,
using the particle in a box model. To calculate the box length, assume
that the molecule is linear and use the value 135 and 154 pm for C=C
and C-C bonds.
What is the wavelength of light required to induce a transition from n
= 4 and n = 5?
solution
The length of the box is a = 4 x 135 pm + 3 x 154 pm = 1002pm 
n2h2
The energy levels are given by En  
8ma 2
The transition is between n = 4 and n = 5

The difference between the energy level is given by the expression

h2
En 1  En (2n  1) 
8ma 2
Substitution of the numerical values results in

En (2 * 4  1)
6.626 x10 J .s 
 34 2

4.800 x10  19 
 9.11x10 kg x10.02 x10
 31  10
m
2
solution
c
To estimate the wavelength we consider the formula  

Arrangement of this equation and

c
c 8ma 2 c
   
 E / h h(n22  n12 )

subsequent substitution of relevant values gives


8 x9.11 x  31 * (10.02 x10m) 2 * 2.998 x 108 m s  1 
  34 2 2
368nm
6.626 x10 J s * (5  4 )
6. Is the function Ae–ax an eigenfunction of the operator d2/dx2 ? If so,
what is the eigenvalue?
Solution
d
The first derivative is
dx
 
Ae  ax  Aae  ax

d
The second derivative is
dx
Aae  ax   Aa 2 e  ax

Since the operation returns the original function multiplied by a

constant, a2, then Ae–ax is an eigenfunction of the operator d2/dx2 with
eigenvalue a2.
7. Explain why the Heisenberg uncertainty principle would be violated
if the harmonic oscillator ground-state energy were zero.
Solution
If the harmonic oscillator ground state energy were zero, the
implications is that the kinetic and potential energies are both zero
(since neither can take on negative values). Therefore the momentum
is exactly zero. Also, from the nature of the potential-energy function,
the total energy can only be zero at x = 0. Therefore, this leads to a
situation where we know the values of the momentum and position
simultaneously and exactly. This is a violation of the Uncertainty
Principle.
8. Calculate the lowest possible energy for an electron confined in a
cube of sides equal to 10 pm.
solution

Given: electron in a box, a = 10 pm,

Required: E

the expression for the energy of a particle in a box is given by

For the lowest energy possible we set n1=n2=n3=1. Using m as the

mass of an electron, we solve for E in each case.


solution
Substitution of a = 10 pm yields


9.
A particle is moving in one dimension between x = a and x = b. The
potential energy is such that the particle cannot be outside these limits
and that the wave function in between is

ψ = A/x

a . Determine the normalization constant A.

b. Calculate the average value of x.

solution


solution



b. To find the average value of x we use 

Since we have normalized the function, 

the denominator becomes 1 and we can solve as,




10. An electron is confined in a one-dimensional box 1 nm long. How
many energy levels are there with energy less than 10 eV? How many
levels are there with energy between 10 and 100 eV?
solution


Solution


11.
Determine whether the eigenfunctions obtained for a particle in a
one-dimensional box are eigenfunctions for the momentum operator.
If they are, obtain the eigenvalues; if they are not, explain why.
Solution

if the operation returns the original function multiplied by a

constant, the function is an eigenfunction.


Since the result is not a constant multiplied by ψn , ψn is not an
eigenfunction of the momentum operator. This conclusion is related
to the Heisenberg uncertainty principle; the position and momentum
operators do no commute, there are no common eigenfunctions, and
the two properties cannot be measured simultaneously and
precisely. However, the eigenfunction ψ n , like any other function,
can be expressed as a linear combination of the set of momentum
eigenfunctions
12. What is the quantum-mechanical probability of finding the
particle in a one-dimensional “box” in the middle third of the “box”?
Derive an expression that shows how this quantity depends on the
quantum number n.
Solution
Given: one-dimensional box Required: probability The quantum
mechanical probability is given by


Since we are trying to find the particle in the middle third of the box,
we consider the region between the first third and the second third
of the box. If the box is of length a, then we have the boundaries a
a/3 and 2/3.

We use the wave function in the form of 


 


13.
Consider, on the basis of the uncertainty principle, the uncertainty in
the energy if the uncertainty in the position is equal to the length of
the side of the cube for an electron confined in a cube. Calculate ΔE
for a cube of sides equal to 10 pm
solution
The uncertainty principle is given as 

*½

We rearrange to obtain an expression for ∆E .

so that *½

Substitution into we write 

which simplify to 
Now, consider that

a = q = 1 x 10-11 m, substitution of this value in the expression for

E we obtain


14. Use the trial function Ψ = x(a – x) to calculate an energy for a
particle in a one-dimensional box of length a,
Solution
Energy is given by The Ĥ operator is

The potential energy, Ep can be set to zero inside the box, and the Del-
squared or Laplacian operator, is given by

For a one-dimensional box,

Solving the denominator and numerator separately provides a much
easier way to obtain the result.
The numerator is,
The denominator is,
 Therefore E is,

Notice that for n = 1, the exact energy is

15. Calculate the wavelength and energy corresponding to the n = 4 to
n = 5 transition in the hydrogen atom.
Solution

we can calculate the wavelength using the Rydberg formula

Energy is determined from E = h

For the evolution of a system with time, it is necessary to solve the
time-dependent Schrödinger equation:


16. In the Balmer series of the hydrogen atom, the first emission line is
observed at 656.3 nm. Calculate the value of the Rydberg constant.
What is the energy of the light quanta emitted during the transition?
Solution

Given: λ = 656.3 nm , Balmer series, 

To find Rydberg’s constant, we can find R using

and the fact that for the Balmer series, n = 3. n1 = 2. 


To find the energy we use,


17.

Consider the following molecules: H2, HCl, CO2, CH4, H2O, CH3Cl, CH2Cl2,
H2O2, NH3, and SF6. Which of them will give

a. a pure rotational spectrum,

b. a vibrational-rotational spectrum,
c. a pure rotational Raman spectrum,
d. a vibrational Raman spectrum?
Solution
18. Analysis of the vibrational-rotational spectrum of the H35Cl
molecule shows that its fundamental vibrational frequency ν0 is
2988.9 cm–1 . Calculate the force constant of the H—Cl bond.
Solution



Solving for k we get,


19. Calculate the ionization energy of the hydrogen atom on the basis
of the Bohr theory.
Solution
The energy required to remove the electron from the lowest energy
level in hydrogen (n1 =1)to infinity, (n2 = ∞) is the ionization energy.
the expression for energy, E = hν
20. The separation between neighboring lines in the pure rotational
spectrum of 35Cl19F is found to be 1.023 cm–1 . Calculate the
interatomic distance.
Solution

Write the expression for the moment of inertia

From which we know that

We first find the moment of inertia using the knowledge of the rotational
constant B


We now calculate the reduced mass using 

Substitution of the numerical values gives


Substitution of all the numerical values into the previous equation we get


21. The lines in the pure rotational spectrum of HF are 41.9 cm –1
apart. Calculate the interatomic distance.
Solution

Write the expression for the moment of inertia

From which we know that

We first find the moment of inertia using the knowledge of the rotational
constant B
We now calculate the reduced mass using

Substitution of the numerical values gives

Substitution of all the numerical values into the previous equation we get
22. In the microwave spectrum of 12C16O the separation between lines
has been measured to be 115270 MHz. Calculate the interatomic
distance.
Solution

Write the expression for the moment of inertia

From which we know that

We first find the moment of inertia using the knowledge of the rotational
constant B
We now calculate the reduced mass using

Substitution of the numerical values gives

Substitution of all the numerical values into the previous equation we get
23. The J = 0 → J = 1 line in the microwave absorption spectrum of
C O and of 13C16O was measured; in its ground vibrational state, the
12 16

former has the value 3.842 35 cm–1 and the latter, the value 3.673 37
cm–1 . Calculate
a. the bond length of the 12C16O molecule,
b. the relative atomic mass of 13C,
c. the bond length of the 13C16O molecule.
Solution. interatomic distance is the same as bond length.

Write the expression for the moment of inertia

From which we know that

For the transition J = 0 → J = 1, ∆ ṽ =2B and therefore

The reduced mass is calculated using

Substitution of all the numerical values into the previous equation we

get
b) the relative atomic mass can be obtained from the ratio of the
rotational constant and the reduced mass μ.

If Mr is the relative mass of 13C, and subscript 1 refers to 12C16O and,

subscript 2 refers to 13C16O, we have,
24. Analysis of the vibrational-rotational spectrum of the H35Cl
molecule shows that its fundamental vibrational frequency ν0 is
2988.9 cm–1 . Calculate the force constant of the H—Cl bond.
The force constant is defined in terms of the fundamental frequency
in