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CHAPTER 9: Quantum Mechanics Applications


-translational, vibrational, rotational motion
I. Translational motion.
A. Single particle in free space, 1-D.
1. Schrodinger eqn


)
H = E



h
2
2m
d
2
dx
2
= E; no boundary conditions
2. General solution:


= Ae
ikx
+ Be
ikx
3. Energy eigenvalues


E =
k
2
h
2
2m
Note: all values of k are permitted, not just integers. Therefore the
energy of a free particle is not quantized. E can take on any (+)
value.
4. Note: can also be written as:
= A sin kx + B cos kx
Since:
e
i
= cos +i sin
e
-i
= cos i sin
B. The particle in a one-dimensional box.
1. The potential function V(x).
V(x) = 0 for 0 < x < L
V(x) =

elsewhere
2
2. Schrodinger equation:



H = E
where


)
H = kinetic energy operator + V(x)



=
h
2
2m
d
2
dx
2
+ V(x)
So we can write:


h
2
2m
d
2
dx
2
(x) + V(x)(x) = E(x)
V(x) = 0 in box
= outside box
Above is equivalent to equation:


h
2
2m
d
2
(x)
dx
2
= E(x) plus boundary condition.
Boundary condition: x restricted to interval from 0 to L (in which case
V(x) = 0) and is required to vanish at x=0 and x=L. Boundary
condition allows us to drop V(x) term.
Now, need to find (x) which is a solution of this differential eqn.
In other words, find a fct such that, if we differentiate with kinetic
energy operator we obtain E; that is a constant times .
Solution:

n
= Bsin
nx
L





n=1, 2, 3,
whole series normaliz. quantum number
of solutions coefficient (state number)

1
,
2
,
3
,&
associated energy eigenvalues


E
n
=
n
2
h
2
8mL
2
3
Problem
Lets check to see if this is a solution:


h
2
2m
d
2
dx
2

n
=
h
2
2m
d
2
dx
2
Bsin
nx
L
[
\
|

)
j
=
h
2
2m
d
dx
Bcos
nx
L
[
\
|

)
j
n
L
=
h
2
2m
B
n
L

( )
sin
nx
L
[
\
|

)
j
n
L
=
+h
2
2m
B
n
L
[
\
|

)
j
2
sin
nx
L
[
\
|

)
j
=
h
2
2m
n
2

2
L
2
|
|
|
|
|
|
Bsin
nx
L
[
\
|

)
j



n
2
h
2
8mL
2

n


= E
n

n
!!!
or
H
n
= E
n

n
Interpretation:
Lowest energy quantum state:
let n=1

1
=
2
L
sin
x
L
; E
1
=
h
2
8mL
2
First excited state
let n=2

2
=
2
L
sin
2x
L
; E
2
=
4h
2
8mL
2
4
Energy level diagram:
Wavefunctions for n=1 thru 5
Limiting conditions:


uniform probability
(just like classical result)
Correspondence principle:
limit (Quantum Results) = Classical results


n
Orthogonality Condition:
If
n
is a correct, well-constructed solution to the Schrodinger
equation, then:


dx
i
*
0
L


j
= 1 if i = j
and


dx
i
*
0
L


j
= 0 if i j

i
is said to be orthogonal to
j
.
5
Illustration of orthogonality. Here multiply n=1 and n=3 wave functions
together and then integrate product from 0 to L. Should get 0.
Practical Applications (particle in 1-D box):
Energy levels of delocalized electrons
in long conjugated molecules:
hexatriene

E
n
=
n
2
h
2
8mL
2
where: E
n
is the energy levels for electrons
m is electron mass
L 6 x carbon-carbon bond length
C= C -- C = C -- C = C
C -- C -- C -- C -- C -- C
Delocalized -bond system
Approximately 1-D
6 electrons
L
Length
6
Spectroscopic transitions in the hexatriene system:
6 electrons fill 3 levels: remember, Pauli Exclusion principle
excludes > 2 e
-
from occupying a given quantum state.
So can use: Particle-in-box to predict -spectrum
Pauli Excl princ
E=h
C. Particle in a 2-D Box (i.e. a particle confined to a surface)
1. Picture
a = length in x-direction
b = length in y-direction
ground
state
n=4
n=3
n=2
n=1
xx
xx
xx
1st excited
state
n=4
n=3
n=2
n=1
x
xx
xx
x
E = h, where is the
frequency of
light promoting
transition
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2. H=E



H =
h
2
2m

2
x
2
+

2
y
2






partial differential equation now
Solved by separation of variables technique (see text).
3.

E
n
x
n
y
=
h
2
8m
n
x
2
a
2
+
n
y
2
b
2








n
x
, n
y
=1,2, 3...

n
x
,n
y
=
4
ab
sin
n
x
x
a





sin
n
y
y
b






4. Special case: Energy level diagram when a=b=L (square box)
5. Attempt to
2
draw pictures.
(1,1) (1,2) (2,1) (2,2)
The above is first example of degeneracy = two or more different wave
functions (quantum states) having the same energy.
e.g., states (1,2) and (2,1)
states (1,3) and (3,1)
Energy (3,1) (1,3) 10h
2
/8mL
2
(2,2) 8h
2
/8mL
2
(2,1) (1,2) 5h
2
/8mL
2
(degeneracy
(1,1) 2h
2
/8mL
2
(n
x
,n
y
)
8
D. Particle in 3-D Box:
1.
c
a b

n
x
,n
y
,n
z
=
8
abc
sin
n
x
x
a





sin
n
y
y
b






sin
n
z
z
c







E
n
x
,n
y
,n
z
=
h
2
8m
n
x
2
a
2
+
n
y
2
b
2
+
n
z
2
c
2








2. Energy level diagram for a=b=c (CUBE)
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II. Vibrational Motion.
A. The 1-D Harmonic Oscillator.
1. An important model for vibration of a diatomic.
V(x) =

1
2
kx
2
where k= bond force constant (stiffness)
x = displacement of bond length b from equilibrium length b
o
x = b - b
o
x = 0 represents bond at its equilibrium distance
F=-kx (Force)
2. Classical trajectory.
x(t) = A sin(2t) (if vibration starts at x=0 moving in (+) direction)
A = amplitude of vibration (can be any value)
= frequency of oscillation


=
1
2
k

lets also define



2 =
k

= reduced mass
=


m
1
m
2
m
1
+ m
2
m
1
m
2
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3. Quantum mechanical Schrodinger Eqn.



H = E

H =

E
K
+

V

E
K
=
h
2
2m
d
2
dx
2
as usual

V =
k
2
x
2
S.E. is then:


h
2
2m
d
2
dx
2
(x) +
k
2
x
2
(x) = E
4. Stationary Solutions: (x)
vibrational quantum number = v = 0,1,2,3
Energies


E
v
= v +
1
2
( )
h
E
v
= v +
1
2
( )
h
=
1
2
h,
3
2
h,
5
2
h
(evenly spaced levels)
where:


=
1
2
k

OR

=
k

Wavefunctions:

x
( )
= N
v
H
v
(y)e
y
2
/ 2
; where y
x

and (
h
2
k
)
1/ 4

N
v
= normalization constant
H
v
(y) = the Hermite polynomials
11
Ground state

o
x ( ) = N
o
e
x
2
/ 2
2
= Gaussian function
symmetric function around x=0
(said to be an even function)

o
x
( )
=
o
x
( )
property of even function
12
1
st
excited state

1
x
( )
= N
1
2x

e
x
2
/ 2a
2
x times Gaussian
an odd function

1
x
( )
=
1
x
( )

1
is odd because:

even function
e
x
2
/ 2
2






odd function
x






= odd function
( )

2
x ( ) = N
2
4x
2

2
2






e
x
2
/ 2
2
even power even power even
of x of x
(even function) (x
0
=1)

2
is even function
13
Here are the first 5 vibrational state wavefunctions:
Here are the probability density functions

14
5. Notes on Parity (symmetry of functions).

0
has even parity

1
has odd parity

2
has even parity

3
has odd parity
etc.
(even function) x (even function) = even function
(even function) x (odd function) = odd function
(odd function) x (odd function) = even function
Integrals:


dx f x
( )

= 2 dx f x
( )
0

if f(x) is even


dx f x
( )

= 0 if f(x) is odd
Very useful in solving certain integrals.
Some functions, however, are neither even or odd parity.
Examples:
Knowing the wavefunctions we can calculate a variety of properties
of the harmonic oscillator in any given quantum state v, such as
average position <x>, average <x
2
>, the average potential energy
<kx
2
/2>. Here < > denotes expectation value.
See text for examples.
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III. Rotational Motion and Angular Momentum.
A. Rotation in Two Dimensions (particle on a ring)
1. Physical picture: particle of mass m constrained to move on a
circular path of radius r in the x-y plane.
2. Treat classically first.
Energy is all kinetic, so classically E = p
2
/2m
Classical angular momentum around the z-axis is J
z
=+ or -pr
So we can write:

E =
J
z
2
2mr
2
=
J
z
2
2I
; where I = moment of inertia
3. Apply quantization condition simply using de Broglie equation


since J
z
= pr
and
=
h
p
then
J
z
=
hr

opposite signs denote opposite directions of travel


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However, not all wavelengths are allowed but only those that exactly
repeat themselves around the ring (satisfy periodic b.c.).
Thus, only wavelengths obeying the following condition will work:


=
2r
m
l
where
m
l
= 0,1,2,.... (here is the angular momentum quantum #)
and so
J
z
= m
l
h
So we have the quantization of
angular momentum.
4. Now what about the energies:


E =
J
z
2
2I
=
m
l
2
h
2
2I
5. The wavefunctions:

m
l
() =
e
im
l

(2)
1/ 2
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B. The 2-Particle Rigid Rotor (rotation in 3-D)
1. Physical Picture.
masses m
1
and m
2
moment of inertia = I = d
2
3-dimensional problem
central force problem
(that is, the 2 particles are held at fixed distance by inwardly
directed forces which counteract centrifugal forces.)
Importance: good quantum mechanical model for rotation of
molecules.
2. Full Coordinate System:
3. Simplifying Features:
Since both particles rotate about a fixed center of mass (C.M.),
knowledge of the position of 1 particle automatically implies position
of 2
nd
particle.
Really a 1-particle problem with an effective mass (called the
reduced mass)


=
m
1
m
2
m
1
+ m
2
18
So:
translational motion of system
2 particle separates as whole (motion of the C.M.)
problem into
internal (rotational) motion
characterized by a single effective
particle of mass confined to
motion on sphere of radius d.
this is the part of interest
The rigid rotor problem is mathematically homologous with a single
particle of mass m= on a sphere of radius r=d.
Still 3-D problem!
4. S.E.
H=E



H =
h
2
2

2
+

V

2
is Laplacian operator:

2
x
2
+

2
y
2
+

2
z
2
(in Cart. Coord.)
V = 0, since particle is constrained to a spherical surface.
5. For convenience in central force problems, convert to spherical polar
coordinates.
r fixed (= d)
19

2
=

2

r
2
+
2
2

r
+
1
r
2
1
sin
2

2
+
1
sin

sin















radial portion
(kinetic energy
of radial motion
= 0 since r=d rigid)
angular portion
=


1
r
2

2









h orbital angular momentum
operator

2
= the legendrian operator
H=E

h
2
2d
2

2
= E
where I = d
2
= moment of inertia of rotor
6. Solution (, ) (function of the 2 polar angles)
(, ) =


Y
l,m
l
,
( )
where Y is special family of functions called
the spherical harmonics
Quantum state can be specified by 2 quantum numbers:
l, m
l
l = 0, 1, 2 orbital angular momentum quantum number
m
l
= -l, 0+l magnetic quantum number
7. Now refer to Table 9-3 in Atkins. (Note: H atom wave functions
have these very same functions times a radial function.)
8. Energies of the rotor.


E = l l + 1
( )
h
2
2I
depend only on l, not m
l
.
(m
l
=-2) -1 0 1 2 l=2
(m
l
=-1 0 +1 l=1
l=0, m
l
=0


E = 2 3
( )
h
2
2I


E = 1 2
( )
h
2
2I


E = 0
20
9. Degeneracy = (2l + 1)
10. Angular momentum J and J
z
.


J = l l + 1
( )
h magnitude of the angular momentum


J
z
= m
l
h angular momentum about the z-axis
21
11. Appearance of spherical harmonics using m
l
=0
22
23
Conversion of notation to the rigid diatomic rotor:
Use


E
J
= J J + 1
( )
h
2
2I
where J= rotational energy level of rotating diatomic
IV. Intrinsic Spin of Microscopic Particles
A. Properties
1. Spin emerges when special relativity is applied to quantum mechanics.
2. Microscopic particles possess an intrinsic angular momentum about their
axis called spin.
3. This is treated differently than orbital angular momentum because it has
different boundary conditions.
4. The magnitude of the spin angular momentum of a particle is determined
by the spin quantum number s, and is given by:


s(s +1) { }
1/ 2
h
5. The value of s for a given type of particle
is fixed. It cannot change. For an electron or
proton, s=1/2.
6. The component of spin angular momentum along
an axis z defined by an external magnetic field
is dictated by the
spin magnetic quantum number m
s
.
m
s
can take on values from -s, -s+1, s-1, s
For an electron or proton with s=1/2
m
s
can take on values -1/2 and +1/2
M J=2
M=-1 0 1 J=1
J=0
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V. Tunneling.
A. Definition: passage of a particle through an energy barrier that exceeds
the energy of the particle. i.e. passage through a classically forbidden
zone.
B. Example.
Classically, the particle of energy E trapped in the well will remain
trapped forever.
In Q.M., it has finite probability of escape.
25
In fact, of the particle has a small contribution through and outside
barrier.
= spatial decay parameter =


2m V
b
E ( )
h
2






1/ 2
C. Transmission probability e
-L
Note that the larger is, the more is damped as it passes through
barrier.
As Transmission Probability
depends on V
b
barrier wt. V
b
Prob
E energy of particle E Prob
m mass of particle m Prob
D. Exact calculation of transmission probability through square barriers can
be obtained by properly piecing together solutions to S.E. in each region.
26
Matching boundary conditions provide us simultaneous eqns to solve to
obtain weighting coefficient for each region.
E. Result:
Transmission Probability

T = 1+
e
L
e
L
( )
2
16 1 ( )










1


=
E
V
where E is the energy of incoming particle, V is barrier height
F. Approx. result in limit of high and long barrier.


L >> 1
e
L
>> e
L
Simplest results:

T 16 1
( )
e
2L
T depends on L, m, E, V
VI. Approximation Techniques.
A. Most interesting systems cannot be solved exactly in terms of known
analytical functions. Two main approximation approaches are used:
1. Variation theory (will introduce with molecular orbital theory)
2. Perturbation theory (here)
B. Time-independent perturbation theory
1. Hamiltonian split into easy part (0-th order part) with known
eigenfunctions and eigenvalues, and the complicating part (the
perturbation):


H =

H
(0)
+

H
(1)
2. Energy eigenvalues are then represented by a series of corrections,
with the o-th term being the eigenvalue of the non-perturbed
Hamiltonian.

E = E
(0)
+ E
(1)
+ E
(2)
+ ...
3. Wavefunctions work the same way, with the o-th order term being
the eigenfunctions of the o-th order Hamiltonian.

=
(0)
+
(1)
+
(2)
+ ...
27
4. It can be shown that the 1
st
order correction to the energy (of the
ground state) can be written as:

E
o
(1)
=
o
(o)*

H
(1)


o
(o)
d
Notice that the 1
st
order energy correction requires only a knowledge
of the 0-th order wavefunction (the unperturbed solution).
It is the perturbation Hamiltonian averaged over the unperturbed
probability distribution.
5. The 2
nd
-order energy correction is a bit more complicated:

E
o
(2)
=
H
no
(1)
2
E
o
(o)
E
n
(o)
n0

where we have introduced the notation often used in QM:


nm
=
n
*



n
d
C. Time-dependent perturbation theory
1. Extremely useful in spectroscopy for calculating transition probability
between quantum states due to electromagnetic wave (light).
2. Perturbation Hamiltonian is now time-dependent:


H =

H
(0)
+

H
(1)
(t)
3. Lets specifically treat the perturbing effect of an oscillating electric
field of frequency and amplitude E interacting with a dipole
moment
z
:


H
(1)
(t) =
z
Ecost
4. It can be shown that the rate of transition between two quantum
states i and f can be written as:

w
f i
E
2

f
*

i
2
The term in absolute value brackets is called the transition dipole
moment, which is central to the understanding of spectroscopy. It
is a measure of the charge redistribution that accompanies a
transition.