Part IB Chemistry A 200405

Introduction to Quantum Mechanics

Examples
Questions marked with one or two asterisks are intended for students who are
more mathematically inclined. Questions marked involve working through
material that is in the notes, so they should be straightforward, but you should
do them anyway to make sure that you understand what is going on.

Fundamentals
1 Show that the harmonic oscillator wavefunction
0
N exp

 km
x2 
2

is normalized if N

km  2  2  1 8 . (Remember that

 x  .)

2 Evaluate x for (i) a harmonic oscillator with mass 100 g and force constant
k
6 N m  1 and (ii) a diatomic molecule with (reduced) mass 1 a.m.u. and
force constant 600 N m  1 .
3 In three dimensions, the kinetic energy T of a single particle is 1  2m  p 2x 
p2y  p2z  . Show that the corresponding operator is

 2 2

2m
























4 Show that if 
E , then t
exp iEt   satisfies the
time-dependent Schrdinger equation.

 5 If   
E   , show that  t 






a

exp
iEk t   satisfies
k k k
k
k k
the time-dependent Schrdinger equation for any constants a k .
T

 6 Consider the time-dependent wavefunction

1
2

a  b  eit  

1
2

b  e 

it 

Show that
a at time t
0, and that
ib at time  2. (First show

that can be expressed in the form
a cos t   ib sin t  .)

7 What is the wavefunction for a free particle with momentum p in the x direction?
8 Show that a free particle with a wave function A sin px     B cos px    has
energy p2  2m, for any values of the constants A and B. Show that such a wavefunction is not in general an eigenfunction of p x .
9 Show that n and m for the particle in a box are orthogonal unless m
n.

10 For a particle in a box of length a, show that the normalizing factor A for the
wavefunction A sin nx  a is 2  a, for any n. What is the expectation value of
the momentum?
11 Using the normalised wavefunction n

2  a sin nx  a  for the particle in a
box, evaluate the expectation values of x, px and p2x ,  and show that x2

 1
1 
2
a
. Hence show that xpx 12  for any n.
2
2
3 2n

 



The Harmonic Oscillator

   km
x2  is an eigenfunction of
2

12 Show that the wavefunction 0
N exp

 2 d2
2m dx2 

1 2
2 kx

How is the eigenvalue related to the classical frequency
1  2  k  m? Find

an expression for x when the potential energy 12 kx2 is equal to this energy eigen1 4
 2  4km
value. Compare this expression with x

.



13 Show that px
   2s for the harmonic oscillator wavefunction 0 , where s

 2  mk  1 4 , and hence that xp
 2. (Note that x
s   2 (see eq. (2.9)
x
in the notes).)
14 Write down the harmonic oscillator wavefunction 1 (without normalising it),
and show that it is orthogonal to 0 .
15 Estimate the probability of finding the harmonic oscillator in its ground state
in the classically forbidden region, i.e., with q
1. (Use tables of the Nor2
mal probability distribution, or plot 0 and estimate the areas by counting
squares.)

16 The separation between the two lowest vibrational energy levels of the HBr
molecule,
0 and
1, is 2559  25 cm  1 , while the separation between
1
and
2 is 2468  83 cm  1 . Calculate  and  xe , and hence estimate De
and D0 using the Morse formula. Compare D0 with the experimental value of
3  75 eV and comment.

Hermiticity and Commutation

 17 Find the Hermitian conjugates of the operators d  dx and id  dx. [Use integration
by parts and remember that the wavefunction goes to zero at infinity.]
 18 Show that the Hermitian conjugate of P Q is Q P . [Use the definition of the
Hermitian conjugate in eq (4.1) of the notes.]
 19 The wavefunctions are normalized eigenfunctions of a Hermitian operator
n
i.e., Q
n
qn n . Show that
n cn n is normalized if n cn 2
1.
Q;

20 Prove the following properties of commutators:

(a) Q  Q

0.



Q  P
.
(b) P Q

(c) P  Q R

P  Q
R  Q P  R
. [ Start from the r.h.s. ]

 21 Use the operator Q (eq. (4.12) in the notes) to find the wavefunction for the
2
harmonic oscillator. (Dont attempt to normalize it.)

 22 The intensity of a transition between states  and  of the harmonic oscillator
is proportional to  q  2 . Express q in terms
 of the ladder operators Q and


 1.
Q , and hence derive the selection rule that 





Angular Momentum
23 Using the Cartesian expressions for the angular momentum operators, show that
Jx  Jy

i  Jz . Deduce that Jy  Jz

i  Jx and Jz  Jx

i  Jy .

24 Using the results of Ex. 20c and Ex. 23, show that Jz commutes with 2 .
25 Show that the spherical harmonics Y10 and Y11 are normalized eigenfunctions of

2
and Jz . (Remember that the volume element is sin d d.)
 26 Show that sinJ eiJ is an eigenfunction of
2 with eigenvalue J J 1  and of

Jz with eigenvalue J.


 27 Show that J  J

J , where J
J iJ . Hence show that J YJM is an
z 

 x  y


2
eigenfunction of
with eigenvalue J J  1 and of Jz with eigenvalue M 1
(i.e. that J YJM is proportional to YJ M 1 ).


28 The equilibrium bond length for HBr is 1.414 . Calculate the rotational constant B for this molecule, and express it in cm  1 . (Take care with the units!)

The Hydrogen Atom

29 Defining r 
r  a0 (so that  r
a0 1  r  ), show that the Hamiltonian for the
hydrogen-like atom becomes

  2
1 2
r

r   2r  2
2r  2 r 

where Eh
e2  40 a0 , a0
40  2  me e2 , and 


E
h



 Z
 
r

  .

30 Complete the energy conversion chart on p. 7, in which a horizontal line connects equal energies in different units. (E.g. insert scale marks for 1 eV, 10 eV,
etc.) Mark in the Examples column the following energies (the values are given
in the units normally used by chemists):
(a) The ionisation energy of the hydrogen atom: 13.6 eV.
(b) The dissociation energy of H2 : 457 kJ mol  1 .
(c) The energy of a visible photon:
500 nm.
(d) The energy required to excite a typical C
O vibration: 1600 cm  1 .
(e) kB T , where T
room temperature, say 300 K, and kB is the Boltzmann
constant = 1  381 10  23 J K  1 .
(f) The binding energy of a typical hydrogen bond: 15 kJ mol  1 .
(g) The height of the barrier to the torsional motion in ethane: 12 kJ mol  1 .
(h) The rotational constant Be for 1 H35 Cl (10  6 cm  1 ) and for OCS
(0  20 cm  1 ).
You will find the necessary conversion factors in the Data Book. You may find
it helpful to keep the completed chart for reference.













exp Zr and R21 r
r exp Zr  2  satisfy
31 Show that the functions R10 r
the radial equation for the hydrogen-like atom with l
0 and l
1 respectively.
32 For the normalized hydrogen 1s orbital  1 2 e  r , calculate, in atomic units,

 

(a) The expectation value r of the distance between the electron and the nucleus;

 

(b) The expectation value r 2 ;





 1 r  ;
(c) The expectation value of the potential energy  V
(d) The expectation value of  2  , the square of the momentum (note that
2T and E
T  V );



 

 

Without doing any calculations, explain why x
0 and px
0. Without

doing any further integrations, evaluate x2 . Hence evaluate x and px , and
verify that the uncertainty principle is satisfied.

 

Many-electron Atoms

 

33 Using eq. (8.5) in the notes, show that V is the same for 2s and 2p in the H
atom.
34 Show that the spin functions 1 2 , 1 2 , 1 2 and 1 2 are eigenfunctions of
the operator Sz
s1z  s2z , and find the eigenvalue MS in each case.
35 Show that the triplet and singlet spin functions are all normalised and orthogonal
to one another.
4

36 Show that
symm

1
2

 a 1  b 2 

antisymm

1
2

 a 1  b 2 


 
 a 2 b 1

and

a 2  b 1  

are normalized if a and b are orthonormal.

37 Find the term symbol (with J value) for the lowest-energy level of each of the
atoms from K to Zn.

The Variation Principle

38 Using the Hamiltonian for the harmonic oscillator in the form of eq. (3.5)
in the
 notes, find the expectation value of the energy for the wavefunction

exp 12 q2  , and show that it is minimised when
1.

 39 The quartic oscillator has the Hamiltonian



 1 d2
2 dq2 

1 4
2q


Find the expectation value of the energy for the trial function exp 12 q2  , and
show that it is minimized when
31 3 .
40 Show that the secular equations for the hydrogen molecule
ion are satisfied by

ca
cb when E
 , and by ca

cb when E
.
 41 Work through eqs. (11.10)(11.20) of the notes without setting S
0. Set
0
to simplify things this is not an approximation, just a choice of the energy
zero. Show that the orbital energies E are  1  S  and  1 S  . What are
the implications for chemical bonding?
42 The L.C.A.O. method can be applied to the orbitals in formaldehyde, H 2 CO,
but the two orbitals involved are the p orbitals of C and O, which have different
values of . Taking O
C  , find the secular equations in this case, and
show that the energies of the orbitals are E
C  12 1   5  .

Homonuclear diatomic molecules

43 The following data are for the low-lying states of the N2 ion:
Term symbol Configuration
2  2 2  1  4 3 
B 2 u
g
u
u
g
2  2 2  2  3 3 
A 2 u
g
u
u
g
2  2 2  2  4 3 
X 2 g
g
u
u
g

2
2
1

re 
1  074
1  1749
1  11642

e  cm  1
2419  84
1903  7
2207  00

Here re is the equilibrium bond length and e is the harmonic frequency. The
neutral N2 molecule has a bondlength of 1  094 and a harmonic frequency of
2359  61 cm  1 .
Explain these observations with reference to the molecular orbital picture of the
bonding in N2 .

 44 The -dependent part of a orbital in a diatomic is exp i  or exp i  .
The operator
for the total angular momentum about the molecular axis is



Lz

i 
. For a configuration which is a closed shell plus two elec1  2
trons in a shell:

(a) Show that the wavefunction exp i 1  2  is an eigenfunction of Lz with

eigenvalue
2. Explain why this wavefunction has to be combined with
a singlet spin function. What is the term symbol?






(b) Show that exp i 1 2 and exp i 1 2  are both eigenfunctions
of Lz with eigenvalue
0. Show that the sum and difference of these
two functions are respectively symmetric and antisymmetric with respect to
interchange of 1 and 2 , and hence construct 1 and 3 functions.

(c) Consider the effect of changing the sign of both 1 and 2 , and hence show
that the complete term symbols are 1 and 3  .

hartree

eV

kJ mol 

cm 

1 0
1000

0 1
100

0  01
10

0  001
1

10 

0 1

10 

0  01

Examples