Introductory Quantum Mechanics

Serway/Jewett chapters 40.8; 41

What are matter waves?
First consider EM radiation
Intensity of a wave is the energy delivered per unit area per unit time.
This may be expressed as:
Intensity ~ (amplitude of the wave)
2
The intensity of EM waves has a natural interpretation in terms of
particles, since these beams may be described as a beam of particles
photons. Intensity in the photon model is:



If N is the [average] density of photons, in the beam (number of photons
per unit volume). Consider the number of photons passing through and
area A per second. The relevant volume of photons is ctA
) )( (
) ( photons) (#
t A
h
I
A
=
v
v
v v
h Nc
t A
h tA Nc
t A
h
I
tA Nc V N
=
A
A
=
A
=
A = =
) )( ( ) ( photons) (#
photons) (#
For light:


Speed of light, c, is a constant
For a given EM wave, photon energy, h, is a constant
The only variable reflecting change in the light intensity is
the average density of photons, N, c and are constants
Therefore,
What are matter waves?
2
wave) the of amplitude ( = v h Nc I
2
wave) the of amplitude ( N
What are matter waves?
N must also be considered from a statistical point
of view. Just as we saw for the cases of partially
reflected light or the energy delivered to a screen.
Need to ask the question:
What is the probability that a photon is reflected or of
finding a given number of photons in a given volume of
the beam?
The answer is:
The probability of finding a number X of photons in a
volume V is given by ratio X/V
The average photon density in this case is
calculated in the same way: N = X/V !
Since, N is also proportional to the square of
the amplitude of the corresponding wave, we
conclude that

The probability of finding
photon within a given volume
of the beam is proportional to
the square of the amplitude of
the wave associated with this
beam
What are the matter waves?
Thus, a wave (or particularly when it what is
waving is abstract, we say wave function)
provides the basis for describing the
probability density of particles in a beam
But not only EM radiation has a dual nature. So
does matter.
Max Born extended this interpretation to the
matter waves proposed by De Broglie, by
assigning a mathematical function, (r,t), called
the wavefunction to every material particle
(r,t) is what is waving
Definition of (r,t)
The probability P(r,t)dV to find a particle associated
with the wavefunction (r,t) within a small volume
dV around a point in space with coordinate r at some
instant t is


P(r,t) is the probability density

For one-dimensional case
dV t dV t P
2
) , ( ) , ( r r + =
dx t x dV t x P
2
) , ( ) , ( + =
Here |(r,t)|
2
=
*
(r,t)(r,t)
Definition of (r,t)
The probability of funding a
particle somewhere in a
volume V of space is
Since the probability to find
particle anywhere in space is 1,
we have condition of
normalization


For one-dimensional case,
the probability of funding
the particle in the arbitrary
interval a x b is

} }
+ = =
V V
V
dV t dV t P P
2
) , ( ) , ( r r
1 ) , (

2
= +
}
space all
dV t r
}
}
+

+ =
+ =
dx t x P
dx t x P
everywhere
b
a
ab
2
2
) , (
) , (
Quantum Mechanics
The methods of Quantum Mechanics
consist in finding the wavefunction
associated with a particle or a system

Once we know this wavefunction we
know everything about the system!
The Uncertainty Principle
Since we deal with probabilities we have to
ask ourselves:
How precise is our knowledge?
Specifically, we want to know Coordinate
and Momentum of a particle at time t = 0
If we know the forces acting upon the particle
than, according to classical physics, we know
everything about a particle at any moment in the
future
But it is impossible to give the precise
position of a wave
A wave is naturally spread out
Consider the case of diffraction
Most of the energy arriving at a distant
screen falls within the first maximum
The Uncertainty Principle
The Uncertainty Principle
Can we know Coordinate and Momentum
(velocity) at some exactly, if we deal here
with probabilities?

The answer in Quantum Mechanics is
different from that in Classical Physics, and
is encapsulated in the Heisenbergs
Uncertainty Principle
Classical Uncertainty
d
Consider classical diffraction
Most of light falls within first maximum
The angular limit of the first maximum is at the
first zero of intensity which occurs at an angle u
set by the condition, d sinu = , so we can say
that the angle of light is between +u and -u
Consider the following:
t t
t u
t u

u
u
4 ~ , 2 ~
2
have, So
2 ~ and , Now
2 ~ sin
2 ~ sin
2
, 1 ~
sin
minimum first at , ~ sin
y
y
y y
k y
k
y
k k y d
k d
d or d
d
A A
A
A
A A =
As the uncertainty in y increases the uncertainty in the y-component of the k-vector
decreases
Classical Uncertainty

~ 4 ~
4 ~ ) (
by 4 ~
t
t
t
y
y
y
p y
k y
k y Multiply
A A
A A
A A
The classical uncertainty relation
The Uncertainty Principle
An experiment cannot simultaneously
determine a component of the
momentum of a particle (e.g., p
x
) and
the exact value of the corresponding
coordinate, x.
The best one can do is
2
) )( (

> A A x p
x
The Uncertainty Principle
1. The limitations imposed by the uncertainty
principle have nothing to do with quality of the
experimental equipment
2. The uncertainty principle does imply that one
cannot determine the position or the momentum
with arbitrary accuracy
It refers to the impossibility of precise knowledge about
both: e.g. if x = 0, then p
x
is infinity, and vice versa
3. The uncertainty principle is confirmed by
experiment, and is a direct consequence of the de
Broglies hypothesis
HOWEVER
Since the wavefunction, (x,t), describes a
particle, its evolution in time under the
action of the wave equation describes the
future history of the particle
(x,t) is determined by (x, t = 0)
Thus, instead of the coordinate and velocity
at t = 0 we want to know the wavefunction
at t = 0
Thus uncertainty is built in from the beginning
Examples:
Bullet
p = mv = 0.1 kg 1000 m/s = 100 kgm/s
If p = 0.01% p = 0.01 kgm/s



Which is much more smaller than size of the
atoms the bullet made of!
So for practical purposes we can know the
position of the bullet precisely
m 10 05 . 1
m/s kg 0.01
s J 10 05 . 1
32
34

=
A
> A
p
x

Examples:
Electron (m = 9.1110
-31
kg) with energy 4.9 eV
Assume p = 0.01% p






Which is much larger than the size of the atom!
So uncertainty plays a key role on atomic scale

A 10 m 10
10 2 . 1
10 05 . 1
kgm/s 10 1.2 0.01%
s / m kg 10 2 . 1 J 10 6 . 1 9 . 4 kg 10 1 . 9 2 2
4 6
28
34
28 -
24 19 31
= ~

=
A
> A
= = A
~ = =

-
p
x
p p
mE p
Physical Origin of the Uncertainty Principle
Heisenberg (Bohr) Microscope
The measurement itself
introduces the uncertainty
When we look at an object we
see it via the photons that are
detected by the microscope
These are the photons that are
scattered within an angle 2 and
collected by a lens of diameter D
Momentum of electron is changed
Consider single photon, this will
introduce the minimum
uncertainty

Heisenberg (Bohr) Microscope


u sin 2
max
ph ph
p p = A
u sin 2
ph ph electron
p p p = A = A
u

u u u
u

h
p
h
p p
h
p
electron
ph electron
ph
2
sin , small for
sin
2
sin 2
= A
~
= = A
=
Trying to locate electron we
introduce the uncertainty of
the momentum
As a consequence of
momentum conservation
Heisenberg (Bohr) Microscope
~(D/2)/L, L ~ D/2 is distance
to lens
Uncertainty in electron
position for small is


To reduce uncertainty in the
momentum, we can either
increase the wavelength or
reduce the angle
But this leads to increased
uncertainty in the position,
since
u

u
2
22 . 1
22 . 1 2
= A
=
= A
electron
elelctron
x
D
D x

u h
p
electron
2
= A
D D L x
electron
= = = A ) 2 )( 2 / ( ) 2 ( u u u
Heisenberg (Bohr) Microscope


h x p
x
h
p
D x
D
h
p
electron
electron
electron
22 . 1 ) )( (
22 . 1
2
22 . 1

2
= A A
A
= A

= A
=
= A

u
u

The Uncertainty Principle

Between energy and time
2
) )( (

> A A t E
EM Waves in Empty Space
From Maxwells equations in differential form
one may derive the following partial derivatives
for the fields in empty space:


The simplest solution for the wave equation is a
sinusoidal wave: E = E
max
sin (kx t)
B = B
max
sin (kx t)
The wave number is k = 2/ ( is the wavelength)
The angular frequency is = 2 ( =1/T is the wave
frequency)
2 2 2 2
2 2 2 2
o o o o
E E B B
and
x t x t
c c c c
= =
c c c c
1
o o
v c

= =
= 2.99792 x 10
8
m/s
Classical Wave Operators
Consider the wave equation for light



For a traveling wave solutions are the
eigenvectors, sin(kx-et), and eigenvalues of the
operator on the left hand side are -k
2

For a standing wave between two reflecting
mirros separated by a distance a, the
eigenvalues are, -k
n
2
= n
2
t
2
/a
2
2
2
2 2
2
) , ( 1 ) , (
t
t x E
v x
t x E
c
c
=
c
c
Between perfectly reflecting walls have solutions for the wave equations:





Solutions satisfying the boundary conditions, E(x=0,a) = 0 require,
sin(ka) = 0. This gives, k
n
a = nt or k
n
= nt/a and e
n
= ck
n
= cnt/a, n =
1,2,3
We may say then that the wave, E(x,t) above is a solution of the wave
equation and that the eigenfunctions of the wave equation are



The eigenvalue of the operator is -k
n
2
= n
2
t
2
/a
2



The eigenvalue of the operator is -e
n
2
/v
2

EM Waves between Reflecting Walls
t kx A t kx A t kx A t x E e e e cos sin 2 ) sin( ) sin( ) , ( = + + =
t x k A t x E
n n n
e cos sin 2 ) , ( =
2
2
x c
c
2
2
2 2
2
) , ( 1 ) , (
t
t x E
v x
t x E
c
c
=
c
c
2
2
2
1
t v c
c
}
-k
n
2
=-e
n
2/v
2
If particles have a wave description then they should
obey a wave equation.
A wave equation has a general form,
where and are each a function of r or t, say is
a function of r and is a function of t
A wave in 1D of a particular k-vector and frequency is
an eigenvector of the wave equation. It will have the
form
k,e
(x,t)=Asin(kx-et). Then

k,e
(x,t) = f(k)Asin(kx-et)

k,e
(x,t) = g(e)Asin(kx-et)
Here f(e) and g(e) are eigenvectors of the respective
operators
If particles have a wave description then they should
obey a wave equation
A wave equation has a general form,
where and are each a function of r or t, say is
a function of r and is a function of t
A wave in 1D of a particular k-vector and frequency is
an eigenvector of the wave equation. It will have the
form
k,e
(x,t)=Asin(kx-et).
Quantum Mechanical Operators
) , (

) , (

2 1
t r O t r O + = +
1

O
2

O
1

O
2

O
1

O
2

O
2

O
For specific boundary conditions only specific values of
k and e, k
n
and e
n
, satisfy the boundary conditions

Physical Quantity Operators
symbol actual operation

Momentum

Total Energy

Coordinate

Potential Energy
Quantum Mechanical Operators
) ( ) (

) (

x U x U x U
x x x
t
i E E
x i
p p
x x


c
c

c
c

Guess
Physical Quantity Operators
symbol actual operation

Momentum

Total Energy

Coordinate

Potential Energy
Quantum Mechanical Operators
) ( ) (

) (

x U x U x U
x x x
t
i E E
x i
p p
x x


c
c

c
c

Motivation?
Wave Function of Free Particle
Since the de Broglie expression is true for
any particle, we assume that free particles
can be described by a traveling wave, i.e. the
wavefunction of a free particle is a traveling
wave
For classical waves:

] sin[ ], cos[ t kx A t kx A e e
Wave Function of Free Particle
However, these functions are not eigenfunctions of
the momentum operator, with them we do not find,


But lets try operating on the following wavefunction
with ,




Get same result of course if operate on




{ } ) exp( ] sin[ ] cos[ ) , ( t ikx A t kx i t kx A t x e e e = + = +
) , ( ) , (

) ( ) ( ) (
t x k kAe ikAe
i
Ae
x i
t x p
t kx i t kx i t kx i
x
+ = = =
c
c
= +



e e e
+ = + = + = + = + = + =
c
+ c
= +
x x
p p
h h
k p
x i
p

t
t
2
2

{ } ) exp( ] sin[ ] cos[ ) , ( t ikx A t kx i t kx A t x e e e = + = +

x
p

Wave Function of Free Particle

Similarly can operate on


with ,











( ) ( ) t x E Ae Ae i i Ae
t
i t x E
t kx i t kx i t kx i
, ) ( ,

) ( ) ( ) (
+ = = =
c
c
= +
e e e
e e
This wave function is an eigenfunction of both
momentum and energy
) exp( ) , ( t ikx A t x e = +
t
i E
c
c
=

Expectation Values
Only average values of physical quantities can be
determined (cant determine value of a quantity at a point)
These average values are called Expectation Values
These are values of physical quantities that quantum mechanics
predicts and which, from experimental point of view, are averages
of multiple measurements
Example, [expected] position of the particle
1 ) ( with , ) ( = =
} }
+

+

dx x P dx x xP x
Expectation Values
Since P(r,t)dV=|(r,t)|
2
dV, we have a way to
calculate expectation values if the wavefunction for the
system (or particle) is known




In General for a Physical Quantity W
Below is an operator (discussed later) acting on
wavefunction (r,t)
}
} }
+

+

+

+ + =
+ + = + + = =
dx t x x t x x
t x t x t x dx t x x dx t x xP x
) , ( ) , (
) , ( ) , ( ) , ( since , ) , ( ) , (
*
*
2 2
| |
}
+

+ + = dx t x W t x W ) , (

) , (
*
Expectation Value
for Momentum of a Free Particle
Generally



Free
Particle
| |
}
} }
+

+

+

c
c
=
(

|
.
|

\
|
c
c
= =
dx
x
x
x i p
dx x
x
i x dx x p x p
) (
) (
) ( ) ( ) ( ) (
*
* *

| | | |
| |
| | | | | | | | p k dx Ae Ae k dx Ae ik
i
Ae p
dx Ae
x i
Ae p
A
dx Ae Ae dx x Ae x
ikx ikx ikx ikx
ikx ikx
ikx ikx ikx
= = = =
(

c
c
=

= = =
} }
}
} }
+

+

+

+

+

* *
*
* 2
n integratio of limits as 0 where
, 1 ) ( with ) (
Properties of the Wavefunction and its First
Derivative
1. must be finite for all x
2. must be single-valued for all x
3. must be continuous for all x
}
+

|
.
|

\
|
c
c
= dx x
x
i x p
x
) ( ) (
*

}
+

= dx x x U x x U ) ( ) ( ) ( ) (
*

}
+

|
.
|

\
|
c
c
= dx t x
t
i t x E ) , ( ) , (
*

Schrdinger Equation
Schrdinger developed the wave equation which can be solved
to find the wavefunction by translating the equation for energy
of classical physics into the language of waves




For fixed energy, we obtain the time-independent Schrdinger
equation, which describes stationary states




the energy of such states does not change with time

n
(x) is an eigenfunction or eigenstate
U is a potential function representing the particle interaction with
the environment
( )
( ) ( ) x E x x U
x
x
m

= +
c
c
) (
2
2
2 2

( )
( ) ( ) x
t
i x x U
x
x
m

c
c
= +
c
c

) (
2
2
2 2
E x U
m
p
= + ) (
2
2
Particle in a box with Infinite Barriers
A particle is confined to a one-dimensional
region of space between two impenetrable
walls separated by distance L
This is a one- dimensional box
The particle is bouncing elastically back
and forth between the walls
As long as the particle is inside the box, the
potential energy does not depend on its
location. We can choose this energy value to be
zero
U(x) = 0, 0 < x < L, U(x) , x 0 and x L
Since walls are impenetrable, we say that
this models a box (potential well) has
infinite barriers
Particle in a box with Infinite Barriers
Since the walls are impenetrable,
there is zero probability of finding
the particle outside the box. Zero
probability means that (x) = 0, for
x < 0 and x > L
The wave function must also be 0 at
the walls (x = 0 and x = L), since the
wavefunction must be continuous
Mathematically, (0) = 0 and (L) = 0

Schrdinger Equation Applied to a
Particle in a Box
In the region 0 < x < L, where U(x)
= 0, the Schrdinger equation can
be expressed in the form



We can re-write it as
( )
( ) ( ) x E x x U
x
x
m

= +
c
c
) (
2
2
2 2

( )
( ) x E
x
x
m

=
c
c

2
2 2
2

( )
( )
( )
( )
2
2
2
2
2
2 2
2
2
2

mE
k
x k
x
x
x
mE
x
x

=
c
c
=
c
c

Schrdinger Equation Applied to

a Particle in a Box
The most general solution to this differential
equation is
(x) = A sin kx + B cos kx
A and B are constants determined by the
properties of the wavefunction as well as
boundary and normalization conditions
( )
( ) x k
x
x

2
2
2
=
c
c
Schrdinger Equation Applied to
a Particle in a Box
1. Sin(x) and Cos(x) are finite and single-valued functions
2. Continuity: (0) = (L) = 0
(0) = A sin(k0) + B cos(k0) = 0 B = 0
(x) = A sin(kx)
(L) = A sin(kL) = 0 sin(kL) = 0 kL = n, n = 1, 2
2
2
2
2
2
2 2
2 2
2
2
8 2 2
) (
2
n
mL
h
n
mL m
n
L
E
m
k
E n
L
k
n
n
n n
|
|
.
|

\
|
=
|
|
.
|

\
|
= =
= =

t
t
t
The allowed wave functions are given by



The wave function for one electron is obtianed by
normalizing the wave function
Schrdinger Equation Applied to
a Particle in a Box
|
.
|

\
|
= x
L
n
A (x)
n
t
sin
|
.
|

\
|
= x
L
n
L
(x)
n
t
sin
2
Particle in the Well with Infinite Barriers
0 1
2
2 2
0
2
0
2
2
2 2
, ) 1 (
2
,
2
E E energy n state ground
mL
E with n E n
mL
E
n
= =
= =
t t
http://www.falstad.com/qm1d/ http://www.falstad.com/mathphysics.html
Electron in the 10nm Wide Well with
Infinite Barriers
Calculate E
0
for L = 10nm = 1010
-9
m



Assume that a photon is absorbed,
and the electron is transferred from
the ground state (n = 1) to the second
excited state (n = 3)
What was the wavelengths of the
photon?
2
2 2
0 1
2
0
2
where ,
mL
E E n E E
n
t
= = =
eV 10 meV 1
meV 75 3 eV 00375 . 0 J 10 6
) 10 10 ( 10 1 . 9 2
) 10 05 . 1 ( 14 . 3
3 -
22
0
2 9 31
2 34 2
0
=
= = ~


=

. E
E
Electron in a 10 nm Wide Potential
Well with Infinite Barriers
E
0
= 3.75 meV
eV 00375 . 0
0 1
= = E E E
ground
eV 0.0338 eV 00375 . 0 9 3
is state excited Third
2
0 3
3
~ = = E E
E
m 41 nm 41333
03 0
1240
eV 030 0 00375 0 0.0338 ) (
1 3
~ ~ =
~ = =
.

. . E E hv
Particle in the Infinite Potential Well
2
2
2 2
th
2

sin
2
state For the
n
mL
E
n
L
x
L
n
n
n
t
t

=
|
.
|

\
|
=
Probability to Find particle in the Right
Half of the Well
2
1
]
2
1
2
[
2
) ( sin
2
] sin
2
[ | ) ( |
2 /
2
2 /
2
2 /
2
= = = = +
} } }
L
L
dx kx
L
dx kx
L
dx x
L
L
L
L
L
L
Average Momentum of Particle in a
Box (Infinite Potential Well)






Can evaluate the integral and show it is zero
Can note that the right hand side is either 0 or imaginary,
but momentum cannot be imaginary so it must be zero
0 ) cos( ) sin(
2
sin
2
] sin
2
[ ) ( ) (
0
0 0
* *
= =
c
c
= +
c
c
+ >= <
}
} }
L
L L
dx kx kx k
i L
dx
x
kx
L
i
kx
L
dx x
x i
x p

Finite Potential Well
The potential energy is zero
(U(x) = 0) when the particle
is 0 < x < L (Region II)
The energy has a finite
value (U(x) = U) outside this
region, i.e. for x < 0 and x > L
(Regions I and III)
We also assume that energy
of the particle, E, is less than
the height of the barrier,
i.e. E < U
Finite Potential Well
Schrdinger Equation


I. x < 0; U(x) = U


II. 0 < x < L; U(x) = 0


III. x > L; U(x) = 0

II
II
E
dx
d
m

=
2
2 2
2

I I
I
E U
dx
d
m

= +
2
2 2
2

( )
( ) ( ) x E x x U
x
x
m

= +
c
c
) (
2
2
2 2

III III
III
E U
dx
d
m

= +
2
2 2
2

Finite Potential Well: Region II

U(x) = 0
This is the same situation as
previously for infinite
potential well
The allowed wave functions
are sinusoidal
The general solution of the
Schrdinger equation is

II
(x) = F sin kx + G cos kx
where F and G are constants

The boundary
conditions , however,
no longer require that
(x) be zero at the
sides of the well
Finite Potential Well: Regions I and III
The Schrdinger equation for these regions is


It can be re-written as


The general solution of this equation is
(x) = Ae
Cx
+ Be
-Cx

A and B are constants
Note (E-U) is the negative of kinetic energy, -E
k

In region II, C is imaginary and so have
sinusoidal solutions we found
In both regions I and III,
and (x) is exponential

E U
dx
d
m
= +
2
2 2
2

2
2 2
2 2
2
) ( 2
where ,
) ( 2

E U m
C C
E U m
dx
d
=

mU
C
2
=
Finite Potential Well Regions I and III
Requires that wavefunction, (x) = Ae
Cx
+ Be
-Cx

not diverge as x
So in region I, B = 0, and
I
(x) = Ae
Cx

to avoid an infinite value for (x) for large
negative values of x
In region III, A = 0, and
III
(x) = Be
-Cx

to avoid an infinite value for (x) for large
positive values of x
Finite Potential Well
Thus, we equate the two
expressions for the wavefunction
and its derivative at x = 0, L
This, together with the
normalization condition,
determines the amplitudes of the
wavefunction and the constants
in the exponential term.
This determines the allowed
energies of the particle
The wavefunction and its derivative must be single-valued
for all x
There are two points at which wavefunction is given by two
different functions: x = 0 and x = L
( ) ( )
( ) ( ) L
dx
d
L
dx
d
L L
dx
d
dx
d
III II
III II
II I
II I
) ( ) (
0 0
) 0 ( ) 0 (




=
=
=
=
Finite Potential Well
Graphical Results for

(x)
Outside the potential
well, classical physics
forbids the presence of
the particle
Quantum mechanics
shows the wave function
decays exponentially to
zero
Finite Potential Well
Graphical Results for Probability
Density, |

(x) |
2

The probability densities
for the lowest three
states are shown
The functions are
smooth at the
boundaries
Outside the box, the
probability of finding the
particle decreases
exponentially, but it is
not zero!
http://phys.educ.ksu.edu/vqm/html/probil
lustrator.html
Tunneling
The potential energy has a constant
value U in the region of width L
and zero in all other regions
This a called a barrier
U is the called the barrier height.
Classically, the particle is reflected
by the barrier
Regions II and III would be forbidden
According to quantum mechanics, all regions are accessible
to the particle
The probability of the particle being in a classically forbidden region
is low, but not zero
Amplitude of the wave is reduced in the barrier
A fraction of the beam penetrates the barrier
http://phys.educ.ksu.edu/vqm/html/qtunneling.html
http://phet.colorado.edu/web-pages/simulations-base.html
More Applications of Tunneling
Resonant Tunneling Device
Electrons travel in the gallium arsenide
They strike the barrier of the quantum dot from the
left
The electrons can tunnel through the barrier and
produce a current in the device
More Applications of Tunneling
Scanning Tunneling Microscope
An electrically
conducting probe with a
very sharp edge is
brought near the surface
to be studied
The empty space between
the tip and the surface
represents the barrier
The tip and the surface
are two walls of the
potential well
Simple Harmonic Oscillator
To explain blackbody radiation Planck
postulated that the energy of a simple
harmonic oscillator is quantized
In his model vibrating charges act as simple
harmonic oscillators and emit EM radiation
The quantization of energy of harmonic
oscillators is predicted by QM
Simple Harmonic Oscillator (SHO)
Lets write down the Schrdinger Equation for SHO
For SHO the potential energy is





Time independent Schrdinger Equation for SHO
in 1D
m
k
x m kx
x U
=
= =
e
e
2 2
) (
2 2 2
( )
( ) ( ) x E x
x m
x
x
m

e
= +
c
c

2 2
2 2
2
2 2

Simple Harmonic Oscillator

Solutions of time-independent Schrdinger
equation for 1D harmonic oscillator





( )
( ) ( ) x E x
x m
x
x
m

e
= +
c
c

2 2
2 2
2
2 2

Simple Harmonic Oscillator

Plancks expression for
energy of SHO

Energy of SHO obtained
from the solution of the
Schrdinger equation
Thus, the Planck formula
arises from the Schrdinger
equation naturally
n = 0 is the ground state
with energy h
tv e
t
v e
2 ;
2
,... 3 , 2 , 1 , 0
2
1
2
1
= =
=
|
.
|

\
|
+ =
|
.
|

\
|
+ =
h
n
h n n E

v nh E=
Term h tells us that
quantum SHO always
oscillates. These are called
zero point vibrations
Simple Harmonic Oscillator
Energy of SHO from the Schrdinger equation



The zero point energy h is required by the Heisenberg
uncertainty relationship
The term of h is important for understanding of some
physical phenomena
For example, this qualitative explains why helium does not
become solid under normal conditions
the zero point vibration energy is higher than the melting
energy of helium
Force between two metal plates
v v h nh E
2
1
+ =
Quantum Model of the
Hydrogen Atom
Potential Energy

Time-independent Schrdinger Equation


Schrdinger Equation in so-called spherical
or polar coordinates
2 2 2
2
here , ) ( z y x r
r
e
k r U
e
+ + = =

|

u u

u u

E
r
e
k
r r r
r
r r m
e
=
(

c
c
+
|
.
|

\
|
c
c
c
c
+
|
.
|

\
|
c
c
c
c

2
2
2
2 2 2
2
2
2
sin
1
sin
1 1
2

E
z y x
e
k
z y x m
e
=
+ +

(
(

c
c
+
c
c
+
c
c

2 2 2
2
2
2
2
2
2
2 2
2

The wavefunction is the function of three variables

now and can be written as



We had one variable (quantum box or simple
harmonic oscillator) one quantum number
Here we can assume that both wavefunction and
energy should in general depend on three
quantum numbers, corresponding to each
coordinate
Wavefunction of the
Hydrogen Atom
( ) ) ( ) ( ) ( , , | u | u g f r R r =
Wavefunction of the
Hydrogen Atom
The three quantum numbers, corresponding to
each coordinate are
n is the principal quantum number; it corresponds
to coordinate r
l is the orbital quantum number; associated with
the coordinate , and determines the magnitude of
the electrons angular momentum, L.
m
l
is the magnetic quantum number; associated
with the coordinate , and it determines the
orientation of L in the magnetic field
The Hydrogen Atom
Thus we can write in general:


Quantum numbers determine the quantum state
Often we say that the electron is in the state (n, l, m
l
)
The energy of the particle in a quantum state
depends on all quantum numbers
) , , ( ) , , (
, ,
| u | u r r
l
m l n
=
l
m l n
E E
, ,
=
The Hydrogen Atom
An electron in a hydrogen atom only has
physically reasonable solutions when E, l and m
l

have the values given indicated below:
l m
n l n l
n
a
e
k
h
m e
E
n
E
E
r r
l
e m l n
m l n
l
l
=
< =
=
= = =
=
..., , 2 , 1 , 0
) i.e. ( 1 ..., , 2 , 1 , 0
... , 3 , 2 , 1
2
8
,
) , , ( ) , , (
0
2
2
0
4
0
2
0
, ,
, ,
c
| u | u
The Hydrogen Atom
The electron energy in the
hydrogen atom depends only on
the principal quantum number, n



Same result as in Bohrs model.
2
0
, ,
n
E
E
l
m l n
=
Hydrogen Atom:
From Bohr to Schrdinger
The electron orbital (angular) momentum is


L is thus quantized
This is more general than the Bohrs Postulate 3, since it
allows for orbits with angular momentum of zero (!!)
For large values of l (l >> 1):



) 1 ( + = l l L
l l l L
l
~ + = ) 1 (
Hydrogen Wavefunction
The Hydrogen Atom:
From Bohr to Schrdinger
1. Remember: Electrons simply
exists within the atom, and we can
only know the probability of
finding the electron at a certain
coordinate
2. Bohrs orbits correspond to the
coordinate, where the probability of
finding the electron is the largest
1. Moreover, Bohrs theory was limited to
the states with highest angular
momentum, l = n 1

The wavefunction gives physical meaning of
the orbits:
The Hydrogen Atom:
From Bohr to Schrdinger
There are no orbits!!!
We describe the electron through
the quantum states
The energy of the electron is
constant when electron in a given
quantum state
Thus, no energy can be taken
from electron by radiation
Why doesnt the accelerating electron emit EMW
when in states corresponding to Bohrs Orbits?
The Hydrogen Atom:
From Bohr to Schrdinger
Since the energy of electron in a hydrogen does
not depend on different l and m
l
(in general for
other atoms it does), It is naturally to assume
that photons are only emitted or absorbed with
energies corresponding to the difference
between various energy sates
(

= =
= = =

2 2
0
2
0
, ,
1 1
... , 3 , 2 , 1 ,
n k
E E E h
n
n
E
E E
k n k n
n m l n
l
v
The Hydrogen Atom
Since, the energy depends only on the principal
quantum number, the energy of an electron in
different quantum states - with the same n, but
different l and/or m
l
is the same
The different sates having the same energy are
called Degenerate States
The number of such states (having the same
energy or energy level) is referred to as
degeneracy of the energy level
In general, the degeneracy arises from the
symmetry in a system

Degeneracy: The Hydrogen Atom
Degree of degeneracy for the hydrogen
depends on value of the principal quantum
number, n
Indeed, the larger n, the more values can l
and, thus, m
l
take on

Degeneracy: The Hydrogen Atom
Example: n = 3 there are 9 states (described
by different wavefunctions) that have the
same energy

2 , 1 , 0 2 , 1 , 0 3 = = =
l
m l n
2 32 322 321 1 32 320 311 1 31 310 300
, , , , , , , ,
2 , 1 , 0 ; 2 , 1 , 0 ; 3

= = =

l
m l n
eV 51 . 1
9
6 . 13
3
2
0
3
~ = =
E
E
Degeneracy
Degeneracy can be lifted if additional
interactions (forces) applied to a system
Consider a hydrogen atom in the magnetic field,
B, applied along z-direction. The energy of
electron is then



This energy now depends on m
l
: we say
degeneracy over m
l
was lifted
How many energy levels with different
degeneracy are there for n = 3?
l
e
nlm
m
m
B e
n
E
E
l
2
2
0

+ =
More Features of the Atomic
Wavefunctions
Electrons in the different quantum states are
unlikely to be found in the same spatial regions
Electrons in the lower angular momentum states
are more likely to be found closer to the nucleus
than those in states with higher angular
momentum
In multi-electron atoms the degeneracy over
angular momentum is lifted and the sates with
the same n but different l have slightly different
energies
Space Quantization
l determines the magnitude of the angular
momentum, L:

m
l
determines orientation of L in space when atom
is in a magnetic field
Taking the magnetic field along z-direction, we can show
that

Thus, not only is the angular momentum quantized, but
also its component in some direction, usually taken to
be the z-direction
) 1 ( + = l l L
l

l z
m L =
Space Quantization
Therefore, L, in an atom, cannot have any
arbitrary orientation (in magnetic field) with
respect to z-direction, but rather have only
discrete orientations: Space Quantization



However, as long as we do not have a
preferred direction (e.g. defined by
magnetic field) space quantization is
meaningless

l z
m L =
Space Quantization: Example, l = 2
Space Quantization: Zeeman Effect
1 1
2
0 ; 0 ; 1
E m
m
B e
E E
m l n
l
e
total
l
= + =
= = =

+ + =
= = =
1
1
0
2
1 , 0 ; 1 , 0 ; 2
2
e
total
l
m
B e
E E
m l n

Space Quantization:
Stern-Gerlach Experiment
Silver atoms studied in
the non-uniform
magnetic field with the
gradient along z-
direction (dB/dz)
Although the atoms are
neutral, they possess a
magnetic dipole, and
the inhomogeneous
magnetic field acts on
this dipole with force
Stern-Gerlach Experiment
The atoms are deflected as they travel through the magnet
The stronger the force, the greater the deflection, and thus
the father away from the center of screen the atoms would
land as detected on the screen

m
dz
dB
m
e
dz
Bm
m
e
d
dz
dU
F
e
e
z
|
.
|

\
|
= = =
2
)
2
(

Bm
m
e
U
m
m
e
L
m
e
B B B U
e
e
z
e
z z z
2
So,
2 2
: atom an in orbit in elelctron an For
: z B B field magnetic a in
dipole magnetic a of U energy, potential Magnetic
=
= =
= = =
=

Stern-Gerlach Experiment
If L
z
is quantized (L
z
= m
l
), as it follows from the
Schrdinger equation, the force F
z
is quantized
Thus, one would observe discrete positions on the
screen where atoms land, and the number of
positions is 2l+1 (The expected number of the
positions is the same as the number of different m
l

numbers)
In classical physics case we would expect smooth
distribution of the positions on the screen
Stern-Gerlach Experiment
Only two lines were observed on the screen
on which the atoms land: one above and one
below of the center !!
Moreover, there were no central line and the distance
from the center to each positions was the same
Stern-Gerlach Experiment
Stern-Gerlach Experiment
Stern-Gerlach experiment indeed showed
discrete nature of the momentum, confirming
space quantization
However, the result contradict quantitative
prediction of the Schrdinger
The experiment by Phipps and Taylor with
hydrogen atoms, where m
l
= 0 (and thus L
z
= 0)
showed the two emission lines in the spectrum,
suggesting that the effect is NOT due to Orbital
Momentum
Thus, there may be a magnetic dipole other than
the one associated with orbital momentum!
The Spin
The idea of an intrinsic magnetic dipole was
first introduced by hand by Uhlenbeck
and Goudsmit as internal orbital
momentum called Spin
The existence of spin and the laws
determining its behavior arise naturally
from the relativistic version of Quantum
Mechanics, developed by Paul Dirac
The Spin
By analogy with the orbital momentum and to explain the
experiments, Uhlenbeck and Goudsmit postulated that
there is a magnetic dipole moment associated with the spin:
the spin angular momentum


This is analogous to the orbital angular momentum


The spin can have only two projections on the z-axis, thus,
explaining the Stern-Gerlach and Phipps-Taylor
experiments
The existence of the spin also explained earlier observations such as
the Fine Structure of Spectral Lines
2
1
; ;
2
1
with , ) 1 ( = = = + =
s s z
m m S s s s S


= = = + = ... ; L ); 1 ( ... ) 1 ( with , ) 1 ( m m n n L
z
The Spin
The Spin is a [quantum] property of the electron.
Spin quantum number is always there
Other quantum numbers can change depending on
the specifics of the potential the electron is in.
For instance:
In hydrogen, in addition to the spin, an electron is
characterized by three quantum numbers n, l, m
l
In a 1D Infinite potential well, in addition to the spin, an
electron is characterized by only one quantum number n
The spin is intrinsic to the electron!
The Hydrogen Atom Wavefunction:
Revisited
Now we need to add another quantum
number, associated with the electron spin
2
1
..., , 2 , 1 , 0
) i.e. ( 1 ..., , 2 , 1 , 0
... , 3 , 2 , 1
) , , ( ) , , (
, , ,
=
=
< =
=
=
s
l
m m l n
m
l m
n l n l
n
r r
s l
| u | u
The Ground State of the
Hydrogen Atom
For the hydrogen ground state we have




Reminder: The hydrogen atom is unusual since
states with the same l have the same energy.
2
1
or
2
1
; 0 ; 0 ; 1
) , , ( ) , , (
, , ,
= = = =
=
s l
m m l n
m m l n
r r
s l
| u | u
The Ground State of Atoms other
than Hydrogen
As soon as an atom contains more than one
electron, the states with different l no longer have
the same energy, and degeneracy over orbital
quantum number is lifted
What is the ground sate of a multi-electron system?
Perhaps in the lowest energy state all electrons in the
atom have the same four quantum numbers
NO!!!
Paulis Exclusion Principle
NO TWO ELECTRONS IN A SYSTEM CAN BE
IN THE SAME QUANTUMS STATE
In other words, no two electrons can have the
same values of the quantum numbers

For atoms these are:

This allows us to understand the Periodic Table
The electron configuration of any atom must
satisfy the Paulis exclusion principle
s l
m m l n ; ; ;
Paulis Exclusion Principle: Atoms
Definitions:
a shell is the set of states with the same n (thus
different l, m
l
and m
s
)
a sub-shell the set of states with the same n and
l (thus different m
l
and m
s
)
Using the rules for the atomic quantum
numbers, we determine that the number of
electrons in
a sub-shell is 2(2l+1)
a shell is 2n
2


Additional Rules for Determining
the Ground State-Configuration
1. The total energy of the electron increases with increasing n
(energy less negative)
2. Within a given shell (a given n), the l = 0 states always have
the lowest energy
3. The energy of the sub-shells generally increases with l :
E
l=0
< E
l=1
< E
l=2
< E
l=3

since electron with lowest value of l can be closer to
nucleus and does not feel shielding of (+)
nuclear charge by () electron cloud
Electronic Configuration of the
Atomic Ground State: Examples
We shall use letters instead of numbers to denote the orbital
quantum number:
l = 0 s; l = 1 p;
l = 2 d; l = 3 f
We shall use superscript above the letter to indicate the
number of electrons in a given sub-shell
Hydrogen (1): 1s
1
Lithium (3): 1s
2
2s
1

Nitrogen (7): 1s
2
2s
2
p
3
Argon (18): 1s
2
2s2p
6
3s
2
p
6


Electronic Configuration of the
Atomic Ground State: Examples
Potassium (19): 1s
2
2s
2
p
6
3s
2
p
6
4s
1
Calcium (20): 1s
2
2s
2
p
6
3s
2
p
6
4s
2
Scandium (21): 1s
2
2s
2
p
6
3s
2
p
6
d
1
4s
2
Note that 3d sub-shell starts to fill in after 4s
sub-shell is filled up
The same is true for 4d vs 5s sub-shells
Electronic Configuration of the
Atomic Ground State: Examples
Nickel (28): 1s
2
2s
2
p
6
3s
2
p
6
d
8
4s
2

Copper (29): 1s
2
2s
2
p
6
3s
2
p
6
d
10
4s
1

Silver (47): 1s
2
2s
2
p
6
3s
2
p
6
d
8
4s
2
p
6
d
10
5s
1

Note that there is no nd
9
state for either Cu, Ag,
or Au (they loose one s-electron from the next
shell)
www.webelements.com
Bees
This should be a learning experience. So lets discuss your
project before the due date
After ~ 600 seconds some bees have reached the boundary
and escaped
Up to this time would expect that the variance of the average
that variance begins to approach the diffusion relation derived
by Einstein,





D is the diffusion coefficient, is the mean free path, and t is
the mean free time
Could you describe one characteristic of the bees motion that
you choose. For example, you could consider the time
dependence of the number of bees escaping per unit time or
the spatial distribution of bees at various times.
t t
2
2 2
3
1
, ince s ,
3
1
0 case, this in since , 6 ) ( ) var(
v D v v D
x Dt x x x x
= = =
= ) ( = ) ( = ) ) ( ( =