Quantum Chemistry

Lecture 2

The Schrödinger
g Equation
q
The Particle in a Box
yp
Uncertainty principle
p

NC State University
Uni e sit
 The Schrödinger equation
for a free particle

The solutions are:

eikx
e-ikx
 The p
particle in a box problem
p
Imagine that a particle is confined to a region of space.
The onlyy motion ppossible is translation. The particle
p has
only kinetic energy. While this problem seems artificial at
first glance it works very well to describe translational
motion in quantum mechanics.
mechanics

0 Allowed Region L
 The solution to the Schrödinger
g
equation with boundary conditions
Suppose a particle is confined to a space of length L. L
On either side there is a potential that is infinitely large.
The particle has zero probability of being found at the
boundary or outside the boundary.

0 Allowed Region L
 The boundary conditions determine
the values for the constants A and B

s will vanish
sin a s at 0 ssincece x = 0 a
and
d ssin 0 = 0
0.
sin will vanish at a if kL = n.
/
e e o e, k = n/L.
Therefore,

 = sin nx
Not L
Normalized !
 The particle in a box has
boundary conditions
(0)= 0 (L)= 0

L
 The solution to the Schrödinger
equation with boundary conditions
The boundary condition is that the wave function will
b zero att x = 0 and
be d att x = LL.
(0) = Asin(k0) + Bcos(k0) = 0
From this condition we see that B must be zero.
This condition does not specify A or k.
The second condition is:

(L) = Asin(kL) = 0 or kL = arcsin(0)

From thi
F this condition
diti we see that
th t kL = n. The
Th conditions
diti
so far do not say anything about A. Thus, the solution
for the bound state is:
n(x) = Asin(nx/L)
Note that n is a quantum number!
The solutions to the p
particle in a box
2 2
 hk
E=
2m
2 n 2
h
L
=
2m
2 2
hn
= 2
8mL
The appearance of the wave functions
Note that the wave functions have
nodes (i.e.
(i e the locations where they
cross zero). The number of nodes is
n-1 where n is the quantum number
f th
for the wave ffunction.
ti Th
The appearance
of nodes is a general feature of
solutions of the wave equation
q in bound states. Byy bound
states we mean states that are in a potential such as the
particle trapped in a box with infinite potential walls. We
will see nodes in the vibrational and rotational wave functions
and in the solutions to the hydrogen atom (and all atoms).
Note that the wave functions are orthogonal to one another.
Thi means that
This th t the
th integrated
i t t d product
d t off any ttwo off th
these
functions is zero.
 The p
probabilityy interpretation
p
The wave function is related to the probability for finding
a particle in a given region of space.
space The relationship is
given by:
P =  2dV

If we integrate the square of the wave function over a

given volume we find the probability
g p y that the particle
p is
in that volume. In order for this to be true the integral
over all space must be one.
1=  2dV
all space

If this equation holds then we say that the wave function

i normalized.
is li d
 The normalized bound state
wave function
For the wave function we have been considering
considering,
all space is from 0 to L. So the normalization constant A
can be determined from the integral:

A sin nx sin nx

L L 2 L 2
2 2 2
1=  dx = dx = A dx
0 0 L 0 L
The solution to the integral is available on the
downloadable MAPLE worksheet. The solution is just L/2.
Thus we have:
Thus,
1=A L ,A = 2 ,A= 2
2 2
2 L L
A you can see the
As th so-called
ll d normalization
li ti constant
t t has
h
been determined.
 The p probabilityy of finding
g the
particle in a given region of space
Using the normalized wave function

x = 2 sin nx
L L
one can calculate the probability of finding the particle
in anyy region
g of space.
p Since the wave function is
normalized, the probability P is a number between 0 and 1.
For example: What is the probability that the particle is
between 0 0.2L
2L and 0 0.4L.
4L This is found by integrating over
this region using the normalized wave function (see MAPLE
worksheet). 0.4L
nx
0.4L

P =  x dx
2
d = 2 sin
2
d  0.25
dx 2
0.2L L 0.2L L
The appearance of the probability 2
 The uncertainty principle
When we measure the properties of very small particles, we
cannot help but affect them. The very act of measuring
ca ses a change in the pa
causes particle’s
ticle’s p
properties.
ope ties The
Therefore,
efo e the
description of the the measurement is a probability rather
than a fixed value. We have seen the Born interpretation of
the square of the wavefunction as a probability density.
The consequence of this is that certain variables are linked
By the uncertainty that is inherent in the measurement.
Position and momentum are two such conjugate variables.
Note that the units of position is the reciprocal of the
momentum (if we factor out Planck’s constant)
constant).
x has units of meter, k has units of meter-1
Momentum is p = hk.
t has units of time,  has units of time -1
Energy is E = h.
 Where is the p
particle in the box?
Since we are using a probability function we do not really
know exactly where the particle is. We know that the highest
probability occurs for the position L/2. We can guess that
this is the average position in the box. However, the
more precisely we specify the location of the particle the
less information we have about how fast the particle is
moving. This is a statement of the famous Uncertainty
Principle.
xp > h/2

Let’s look at the Uncertainty Principle using the particle-in-

a-box example. If we know that the particle is in the lowest
level then Uncertainty in its position is approximately equal
to the width of the probability distribution.
The location of a particle in free
space is not defined
Consider a superposition of a wave
with moment hk and h(1.1k)
The sum has a characteristic envelope
f
frequency att ((2 - 1)/2
Envelope
The sum has a characteristic beat
f
frequency att ((2 + 1)/2
Beats
As we add more frequencies we
can speak of a bandwidth k
k = 0.1

3 added cosines
 As the bandwidth increases the
po ition in x-space
position p e be
becomes
ome mo
moree defined

k = 0.2

5 added cosines
The superposition of waves in space
l d to
leads t the
th description
d i ti off a location
l ti

k = 0.7

15 added cosines
 Relevance of the example
Although the function used in the example is periodic it is
relevant. Since in a g given region
g of space
p (i.e.
( where a
measurement can be made) the probability of observing
the particle in a given region of space is dependent upon
the number of contributing waves.
waves If more waves
contribute then the momentum of the particle is less
certain. Thus, the we can know that moment precisely if
we are totally
t t ll uncertain
t i off th
the position.
iti As
A we begin
b i to
t
specify the position more precisely we find that the
momentum is less well known. Since p = hk,, we can
also express this condition as:
xk > 1/2
 Fourier transform related pairs
Position and momentum are related by a Fourier
transform.
x p
Time and energy are related by a Fourier transform.
t E
There is an uncertainty relationship for both of these
related pairs. Thus, for time and energy we have

t E > h/2

as well. These pairs can be related by a probability

function that gives the width of the distribution in each
space Gaussian functions are particularly useful since
space.
the Fourier transform of a Gaussian is also a Gaussian.
 Gaussian Functions
A Gaussian function has the form exp{ -(x – x0)2 }.
The Gaussian indicated is centered about the point x0.
Th Fourier
The F i transform
t f off a G
Gaussian
i iin x-space is
i a
Gaussian in k-space. Since p = hk we also call this
momentum space.p The figure
g shows the inverse
relationship.

x k
 Question
Which of the following represents the hamiltonian?

A hk
A.
2 2
B. k
h
2m
C. – h 2
 2

2m x 2
D. – ih 

x
 Question
Which of the following represents the hamiltonian?

A hk
A.
2 2
B. k
h
2m
C. – h 2
 2

2m x 2
D. – ih 

x
 Question
What is the hamiltonian?

A it is
A. i the
th energy

B. it is the momentum

C. it is the energy operator

D. it is the momentum operator

 Question
What is the hamiltonian?

A it is
A. i the
th energy

B. it is the momentum

C. it is the energy operator

D. it is the momentum operator

 Statistical averaging over
translational energy levels
Quantum mechanics must agree with classical
physics (mechanics) at high temperature or
when the average quantum number becomes very
large. This is the case for translational energy
levels since the spacing of those levels is very
small compared to thermal energy, kT.

Here, we consider how to average over the

energy levels given by the particle-in-a-box
solutions.
l ti
The translational partition function
The translational partition function consists of
a sum over a very large
l number
b off states
t t


q= 
n=1
e (n 2–1)
–(n 1)
= e (n 2–1)
–(n 1)
d
dn
1

This sum can be expressed as an integral over

the states n. The integral can be expressed as
a Gaussian.
Energies from particle in the box can be
used to calculate energy level spacing
The difference in energy levels n in the particle
particle-
in-the-box solutions has the general form.
2
n = h 2
n –1
2
8mX
where n gives the energy of a large number of
translational energy levels derived from the
particle in the box solutions. We can write
 = h2/8mX
/8 X2 to
t use a factor
f t ini the
th Boltzmann
B lt
distribution, so that n = (n2 - 1)
The translational partition
function is a Gaussian
Th Gaussian
The G i in t tto 1/2/2.
i n iintegrates
t /2
 

d == 1 
1/2 1/2
n 2 n
d = 1
–n 2x 2
–x
e dn

e-x
e dx
2 
0 0

Substitute for  to obtain

1/2
2m
qx = 2 X
h
The translational partition function
in three dimensions X,Y, and Z
The volume is V = XYZ


3/2 3/2
2
q= 2 m XYZ
XYZ= 2m V
h h
2

This expression for the translational partition

function derived from the particle in the box
is the same as that derived classically from
the integral over all velocities
velocities.
 The translational partition function
can be expressed in terms of a
thermal wavelengthg 
3/2
q= 2mkT V
V= 3
h 2

where the thermal wavelength is defined as:

= 2mkT
2
h
 Free electron model
for electronic spectra
Before the advent of computers, models such as
particle-in-a-box were used for linear polyenes.
The idea of such a model is that the electrons
from the p-orbitals
p orbitals in a molecule
are particles and the molecule
is the “box”. For example, we
can think of ethylene as a short
box with two electrons as shown
in the figure. Although there are
an infinite number of states, only
two of them are really important
in ethene since there are only two electrons. The
HOMO and LUMO are shown on the left and the
representation of the two lowest electronic states is shown.
 Polyenes

The first four members of the

class of polyenes are shown.
We can treat the p-system of
these molecules using the model
with 2, 4, 6 and 8 electrons,
respectively. As a general rule
the model can be applied to any
number of p-orbitals, with the assumption each p-orbital will
contribute one electron to the total. Then we populate the
levels calculated using the particle-in-a-box and determine
the transition between the HOMO and LUMO. This is
illustrated for butadiene on the next slide.
A B C
Application to aromatic
molecules:
l l b
benzene
NODES
3

0
We can construct molecular
orbitals of benzene using the
six electrons in  orbitals
H

C
H H
C C

C C
H H
C
H Electrons are
spin-paired

Benzene Structure Electronic Energy Levels

 The Free Electron Model Applied to
Benzene
The  system approximates circular
electron path
path.
H

C
H
C C
H
-5 5

C C
H H
C -4
4 4
H

– h 2
 2
 = E -3
3 3
2meR 
2 2 m=3 m=1
-2 2
2 2
E= h m ,  = 1 e im
i  -1
1 1
2meR 2 2 m=0
 The Perimeter Model
The aromatic ring has 18 electrons.
The  system approximates circular
electron path
path.

N N 5
-5
m=9 m=1
N N
-4
4 4

– h 2
 2
 = E -3
3 3
2meR 
2 2
-2 2
2 2
E= h m ,  = 1 e im
i  -1
1 1
2meR 2 2 m=0
 Porphine orbitals

eg eg

a2u
2 a1u
1
Nodes in Porphine orbitals
 The four orbital model is used to
represent the highest occupied and
lowest unoccupied MOs of porphyrins


The two
Th t hi
highest
h t occupiedi d eg 
orbitals (a1u,a2u) are nearly
equal in energy
energy. The eg
orbitals are equal in energy. M1
Transitions
a s t o s occu
occur from:
o
a1u eg and a2u  eg.
a2u  a1u 
 The transitions from ground state  orbitals
a1u and a2u to excited state * orbitals eg
can mix by configuration interaction

Two
T o electronic
elect onic ttransitions
ansitions eg  

are observed. One is very

strong (B or Soret) and the
other is weak (Q). M1 M2
The transition moments are:
MB = M1 + M2
MQ = M1 - M2  0 a  a1u 
2u
Absorption spectra for MbCO and deoxy Mb
Soret Band Q Band

The spectrum of the heme has two bands. The B band or Soret
Band is allowed and therefore intense. The Q band is forbidden.
It is observed because of vibronic coupling with the Soret band.