Basic Modern Physics

5. Quantum Mechanics

Outline

Quantum Mechanics
The Wave Equation
Schrödinger Equation
Linearity and superposition
Expectation values
Operators
Schrödinger Equation: Steady state form
Particle in a box
Finite potential wall
Tunnel effect
Harmonic oscillator
 The Birth of QM
Bohr’s theory,
– Applies to only hydrogen and one-electron
ions
– Cannot explain why certain spectral lines are
more intense
– Cannot account for the observation that many
spectral lines actually consist of several
separate lines
– Cannot explain many aspects of atomic
interaction and physical/chemical properties

Birth of quantum mechanics: The result of

endeavors to generalize the Bohr’s theory
– Major contributors include Erwin Schrödinger,
Werner Heisenberg, Max Born, Paul Dirac… (in
the year between 1925 – 1926)

Major players

5th Solvay conference in 1927

Max Planck, Albert Einstein, Niels
Bohr, Louis de Broglie, Max Born,
Paul Dirac, Werner Heisenberg,
http://www.youtube.com/watch?gl=GB&hl=en-GB&v=8GZdZUouzBY Wolfgang Pauli, Erwin
Schrödinger, Richard Feynman.
 Classical vs quantum mechanics
Classical mechanics is an approximate version of quantum mechanics

Classical (Newtonian) Mechanics Quantum Mechanics

Future history of a particle is Future characteristics cannot be

completely determined by its initial predicted precisely since the initial
position/momentum + forces state of a particle cannot be
Work very well for describing established with sufficient accuracy
“macrosopic” objects, but fails to (Uncertainty principle)
explain ultimately small, or fast things QM only explores “probabilities”
(such as electron, velocity of light)

Laws of classical mechanics thus follow from laws of quantum

mechanics at the limit of large systems or large quantum
numbers
Many “macroscopic” properties of “classic” systems are direct
consequences of quantum behavior of its parts.

The World of Quantum

The World of the ‘Most’, not ‘Absolute’
hydrogen atom

5.3  10 -11m : Most Probable Radius

(Electron is not always observed at exactly 5.3
 10 -11m away from the hydrogen nucleus)

There is only
- Classical mechanics : a single theory
just an approximate version of quantum mechanics. that satisfies for
both macroworld
- Ordinary objects : consist of so many individual atoms and microworld.
→ Departures from average behavior are unnoticeable. → Quantum Theory
 Wave Function
The Quantity which Quantum Mechanics is Concerned with

What is a wave function(Ψ)?

def : The quantity whose variations make up matter waves

- |Ψ|2 : the probability of finding a body at a particular place at a particular time.

(Ψ itself has no physical interpretation)

The problem of quantum mechanics

: Determining Ψ for a body when
its freedom of motion is limited by the action of external forces.

Wave function :   A  iB Complex conjugate :   A  iB |  |2  A 2  B 2

real part complex part

Normalization
Sum of Probability Should Be 1

- |Ψ|2 : Proportional to the probability density P of finding the body

What is normalization?
def : Let |Ψ|2 be equal to the probability density P to
sum of P become 1
 
Normalization : |  |2 dV  
P dV

- The probability of finding a particle between x1 and x2 is described by

x2
Probability : Px1x2   |  |2 dx (1 dimensional case)
x1
 Well-Behaved Wave Functions
Characteristics of Well-Behaved Wave Function

3) Ψ must be normalizable,
   which means that
2) x , y , z must be Ψ must go to 0 as
continuous and x →  , y →  , z →  
single-valued 2
in order that  |  | dV
1) Ψ must be continuous
everywhere. for over all space
and single-valued
everywhere. be a finite constant.

The Wave Equation

Review the Wave Equation

- Free Particle : A particle that is not under the influence of any forces and therefore
pursues a straight path at constant speed

Undamped (constant amplitude A),

monochromatic(constant angular frequency ), harmonic wave
x
 j ( t  )
The form of a free particle wave equation : y  Ae 
(Ch. 3.3.)
Because ei  cos   i sin  ,
x x
y  A cos  (t  )  iA sin  (t  )
 
 Basic Solution of Wave Equation
Derived from Standard Form of Wave Equation
A standard form of wave equation
x
partial derivative  j ( t  ) partial derivative
y  Ae 
 
x t
y i y
 y  iy
x  t

 2 y i 2 2 2 2 y 2 2
 y   y  i  y   2 y
x 2 2 2 t 2

2 y 1 2 y

x 2  2 t 2

Schrödinger’s Equation : Time Dependent Form

A Basic Principle of Quantum Mechanics

A basic form of wave function

x
 i ( t  )
  Ae 
  2v,   v  2v
 k
 v
  Ae 2i ( vt  x /  )

i E   , p  k
 ( Et  px )
  Ae h
  Ae  i (t  kx )
 Basic Form of Schrödinger Equation
Time Dependent Form of Schrödinger Equation
2 
i
x 2  ( Et  px ) t
  Ae 

 2 p2  iE
 2   
x 2
 t 

 2  
p 2    2 E  
x 2 i t

Total E = Kinetic E + Potential E

p2 p 2  2  2
E  U ( x, t ) E   U i     U
2m 2m 2 m x 2
Time-dependent Schrödinger equation in 1-dimension
2  2  2  2
*Time-dependent Schrödinger equation in 3-dimension : ih    (  2  2 )  U
2m x 2 y z

Validity of Schrödinger’s Equation

Schrödinger’s equation cannot be derived from other basic

principles of physic; it is a basic principle in itself.

What we must do is postulate Schrödinger’s equation,

solve it for a variety of physical situations, and compare the
results of the calculations with the result of experiments.

What has happened is that Schrödinger’s equation

has turned out to be remarkably accurate in
predicting the results of experiments.

Schrödinger’s equation does not increase the number of

principles needed to describe the workings of the physical world.:
for example, F=ma can be derived from Schrödinger’s equation.
 Linearity and Superposition
Linear Characteristics of Wave Functions Probability
density
function 2
Linearity of wave function Ψ2
open
If Ψ1 and Ψ2 is solution of slit 2
only
the wave equation

Probability
density
Ψ = a1Ψ1+a2Ψ2 is open
slit 1 function 1
also a solution only
* a1, a2 : constants
Ψ1

Superposition of Wave Function

Wave Functions add, not Probabilities

PDF 2 case 1 : add probabilities only

(slit 2 open)
How to add?
|Ψ1|2+|Ψ2|2

case 2 : add wave functions

P = |Ψ1+Ψ2|2
PDF 1
(slit 1 open)
= |Ψ1|2+|Ψ2|2
+Ψ*1 Ψ2+ Ψ*2 Ψ1

responsible for the oscillations of

an electron intensity at the screen
 Expectation Values
Extract Information from a Wave Function
What are expectation values?
def : The predicted mean value of the result of an experiment.
Discrete Variable Continuous Variable

x
N x i i
x
 P x dx
i i

Ni  P dx
i

wave function is continuous!

- The probability Pi : The probability of finding particle in an interval dx at xi
Pi  | i |2 dx
The particle wave function evaluated at x = xi.

- The expectation value of the position of the single particle :


 x |  | dx
2
Normalization 
 x  
 x   x |  |2 dx

 |  | dx  1
 2
 |  | dx 
2
 

- Can be used to obtain expectation value of any quantity <G(x)>


 G ( x)   G ( x) |  |2 dx For example, U(x)


Uncertain Value’s Case

The expectation value <p> for momentum cannot be
calculated this way because, according to the
uncertainty principles, no such function as p(x) can
exist.

If we specify x, so that Δx = 0, we cannot specify

a corresponding p since ΔxΔp  ħ/2.(Uncertainty
Principle)

The same problem occurs for the expectation value

<E> for energy because ΔEΔt  ħ/2.

→ How are <p> and <E> determined?

: by using an operator!
 Operators
Another Way to Find Expectation Values
What is an operator?
def : A function which acts on functions to produce other functions;
Tell us what operation to carry out on the quantity that follows it.
 i  
 p p 
i
 ( Et  px ) x  i x
  Ae 

 i 
  E E  i 
t  t

  
Momentum Operator : pˆ  Total Energy Operator : Eˆ  i
i x t

  2
Eˆ  Kˆ E  Uˆ i  U
t 2m x 2
Schrodinger Equation
p2 1   2  2
Kˆ E   ( )     2
2m 2m i x 2m x 2 i   U
t 2m x 2

Operators and Expectation Values

The Expectation Value for Momentum and Energy
The expectation value for momentum :
      
 p     * pˆ dx    * ( )dx    * dx
  i x i   x

The expectation value for energy :

    
 E     * Eˆ dx    * (i )dx  i   * dx
x x

When differential operators are involved,

the correct order of factors must be observed.

The expectation value of an operator :


 G ( x, p )     * Gˆ dx


G : Every observable quantity characteristics of a physical system

Schrödinger’s Equation : Steady-State Form
Steady-state Schrödinger Equation in 1-Dimension
- In a great many situations the potential energy of a particle
does not depend on time explicitly. time-dependent
function
  Ae  ( i /  )( Et  px )
 Ae  ( iE /  ) t  ( ip /  ) x
e  e  (iE /  )t
position-dependent
function

h 2 (iE /  )t  2
Substitute in Schrödinger Equation : Ee (iE /  )t   e  Ue (iE /  )t
2m x 2
- The time variations of all wave functions of particles acted on by forces
independent of time have the same form as that of an unrestricted particle.
 2 2m
Steady-state Schrödinger equation in 1D :  ( E  U )  0
x 2  2
 2  2  2 2m
* Steady-state Schrodinger equation in 3D : x 2  y 2  z 2   2 ( E  U )  0

Property of Schrödinger’s Steady-state Equation

Solutions of Schrödinger Equation

- If Schrödinger’s steady-state equation has one or
more solutions for a given system, each of these
wave functions corresponds to a specific value of
the energy E.

- The displacement y always be zero at both end of

the string.
2L
n  n  0,1,2,3...
n 1
- Solutions of Schrodinger’s equation is familiar with
the standing waves in a stretched string of length L.
→ ψ and its derivatives are
continuous, finite, and single-valued
 Eigenvalues and Eigenfunctions
Definition of Eigenvalues and Eigenfunctions

What is an Eigenvalue?
def : The values of energy En for which
Schrödinger’s steady-state equation can be solved.

What is an Eigenfunction?
def : An eigenfunction of a linear operator, G, defined on
some function space is any non-zero function ψ in that space
that returns from the operator exactly as is.

Operator Eigenvalue
Eˆ n n  En n

Eigenfunction

Some Examples
Hydrogen atoms
- the discrete level of energy levels are an example of a set of
eigenvalues
me 4 1
En   2 2 ( 2 ) n = 1, 2, 3,..
8 0 h n
- Eigen values of the total angular momentum
L  l (l  1)

- Dynamical variable G may not be quantized: the measurement does not yield a
unique result but a spread of values with average expectation values

 G    G  dx
2

 Operators and Eigenvalues
Eigenvalue and Hamiltonian Notation
A certain dynamical variable G be restricted to the discrete values Gn.
→ G is quantized

Eigenvalue equation : Gˆ  n  Gn n

→ Any measurement of G can only yield one of the values Gn.

Hamiltonian
: An expression for the total energy of a system in terms of
coordinates and momenta only.

2  2
Hamiltonian Operator : Hˆ   U Schrodinger’s equation : Hˆ  n  En n
2m x 2

Operators and Quantities

Operators Associated with Various Observable Quantities

Quantity Notation Operator

position x x
 
linear momentum p i x
potential energy U (x) U (x)
kinetic energy 2  2
KE 
2m x 2

total energy E i
t
total energy 2  2
H   U ( x)
(hamiltonian form) 2m x 2
 Particle in a Box
The Simplest Quantum-mechanical Problem
Infinite Potential Well :
electron cannot have infinite energy
→ψ=0

wave function exist only inside of this range

* A particle does not lose energy when it collides with walls.(total energy is constant!)

On the inside, Potential energy U becomes a constant (Say 0 for convenience)

Schrodinger’s equation inside of the box :

d 2 2m
 E  0
dx 2  2

Solution for Schrödinger Equation

Solution for Schrödinger Equation of Particle in a Box

d 2 2 m
Schrödinger Equation of Particle in a Box :  2 E  0
dx 2 
by boundary condition
2mE 2mE cos 0  1
A possible solution :   A sin x  B cos x
 

2mE
Considering boundary condition : L  n (n  1,2,3...)


n 2 2  2
Particle in a box : En  n  1,2,3...
2mL2
 Wave Functions
Derivation of the Wave Function of the Particle 2mE n

 L
ψ3
2
2mEn nx
L  n  A sin x (Ch 5.8)  n  A sin
 L

ψ2 - Normalization of wave function ψn

1  cos 2ax
 L sin 2 ax 
 |  | dx   |  | dx  1
2 2 2
 0
ψ1
L nx A2  L L 2nx 
  sin 2 ( )dx    dx   cos( )dx 
0 L 2  0 0 L 
L
2
A2  L L 2nx  L
2  0
|ψ3|2 L  x( ) sin  A2  )  1
2n L  0 2

|ψ2|2  2
To satisfy  | n |2 dx  1 , A
L

|ψ1|2 2 nx
The wave function of the particle in a box : n  sin n  1,2,3...
L L

Momentum Eigenvalues for Trapped Particle

Derivation of Momentum Eigenvalues for Trapped Particle

Expectation value for <p> :

2 nx d 2 n nx
 *  n  sin   cos
L L dx L L L 1
 sin ax cos axdx  2a sin
2
ax
  d 
 p    * pˆ dx    * ( ) dx
  i dx
L
 2 n L nx nx  nx 

i L L 
0
sin
L
cos
L
dx  sin 2
iL  L  0
0

Momentum eigenvalues for trapped particle :

p2 n
E  pn   2mEn  
2m L
n n
( )  ( )
pav  L L 0
* 2
Momentum Eigenfunctions for Trapped Particle

Derivation of Momentum Eigenfunction for Trapped Particle

e i  e  i 1 i 1  i
sin    e  e
2i 2i 2i
Eigenvalues equation : pˆ  n  pn n
2 nx
The wave function of the particle in a box :  n  L
sin
L
n  1,2,3...

2 1 inx / L inx / L
 (e e )
L 2i

Momentum eigenfunctions for trapped particle :

1 2 inx / L
 n  e
2i L
1 2 inx / L
 n  e
2i L
pˆ  n  pn n
*
h d  h 1 2 in inx / L nh  nh
n  e   n  pn n pn  
i dx i 2i L L L L
nh
also, pn  
L

Momentum Eigenfunctions for Trapped Particle

Derivation of Momentum Eigenfunction for Trapped Particle

e i  e  i 1 i 1  i
sin    e  e
2i 2i 2i
Eigenvalues equation : pˆ  n  pn n
2 nx
The wave function of the particle in a box :  n  L
sin
L
n  1,2,3...

2 1 inx / L inx / L
 (e e )
L 2i

Momentum eigenfunctions for trapped particle :

Condition 1 : pˆ  n  pn n Condition 2 : pˆn  pnn
     

h d  h 1 2 in inx / L nh  h d  h 1 2 in inx / L nh 

n  e   n  pn n n   e   n  pn n
i dx i 2i L L L i dx i 2i L L L

nh 1 2 inx / L nh 1 2 inx / L

pn    n  e pn    n  e
L 2i L L 2i L
 Finite Potential Well
Case 1 : Condition for Inside Potential Well
- In the real world : potential wells have definitely
finite potential barrier.
Finite Potential

non-zero

Wave function of the inside potential well :

2mE 2mE
In region II : II  A sin
h
x  B cos
h
x

In this case, ψII  0 at x=0 and x=L,

so both sine and cosine solutions are possible.

Penetration of Electron
Case 2 : Condition for Outside Potential Well

In region I and III :d 2

2
2m 2m(U  E )
 ( E  U )  0 a
dx h h

d 2 real exponential!
 a 2  0 x  0 or x  L
dx 2

Wave function of the outside potential well :

lim e  ax  
 I  Ce ax  De  ax since x (Ch. 5.1. Wave function should have
 III  Fe ax  Ge  ax since lim e ax   a finite value to be normalizable)
x 

 I  Ce ax at x  0   2  C (Ch. 5.1. Wave function and its

 III  Ge  ax at x  L   2  L first derivative should be continuous)
 Tunnel Effect
A Particle Can Tunnel Through a Potential Barrier
What is a tunnel effect?
def : A particle’s ability to penetrate a potential barrier
even though it does not have enough energy
X
to pass over a barrier
O
1
possibilit y of penetration 
width of barrier
1
incoming particle possibilit y of penetration 
height of barrier
penetrate
reflected particle particle Possibility of penetration is very small, but not zero.

Approximate transmission probability : T  e 2 k 2 L

2m(U  E )
k2 
h
L = width of barrier

Scanning Tunneling Microscope (STM)

- STM moves the probe across the surface in

a series of closely spaced back and forth scans
in about the same way an electron beam
traces out an image on the screen of
a television picture tube.

- The probe of STM is controlled precisely

by its piezoelectricity.
(mechanical stress ↔ electric field)

- Actually, the result of an STM scan is

not a true topographical map of surface height
but a contour map of constant electric density
on the surface.

G. Binnig et al, PRL, 49 52 (1982)

 STM image gallery
Si(111) 7x7

Quantum mirage

Don Eigler, IBM

Manipulation of atoms by STM

Xe on Ni(110)

Atom-by-atom chemistry

D. Eigler et al, Nature 344, 524 (1990)

 Harmonic Oscillator
For a Vibration System
What is a harmonic motion?
def : A periodic motion that is neither driven nor damped.
A body in simple harmonic motion experiences a single force which is given
by Hooke’s law

Hooke’s Law
The Case that the Restoring Force on a Particle of Mass is Linear
What is Hooke’s Law?
def : The extension of a spring is in direct proportion with the load
added to it as long as this load does not exceed the elastic limit.

F  kx
x : The displacement of the end of the spring from its equilibrium position
F : The restoring force exerted by the material
k : The force constant (or spring constant)

From F = ma,

d 2x d 2x k A common solution : x  A cos(2vt   )

 kx  m 2  x0
dt dt 2 m 1 k
Frequency of harmonic oscillator : v 
2 m
The Potential Energy of a Harmonic Oscillator

The Case that the Restoring Force on a Particle of Mass is Linear

Any restoring force which is a function of x can be expressed
in a Maclaurin’s series about the equilibrium position x=0 as

 dF  1  d 2 F  2 1  d 3F 
F ( x)  Fx 0    x   2  x   3  x  ...
3

 dx  x 0 2!  dx  3!  dx  x 0
→ x is very small, so it is neglected.
 dF 
F ( x)    x
 dx  x 0

The potential energy function U(x) that corresponds to a Hooke’s law force
x x 1 2
U ( x)    F ( x) dx  k  x dx  kx
0 0 2

Energy Levels of Harmonic Oscillator

1. The allowed energies will not form a continuous

spectrum
but instead a discrete spectrum of certain specific
values only.

2. The lowest allowed energy will not be E=0

but there will be some definite minimum E=E0.

3. There will be a certain probability that

the particle can penetrate the potential well
it is in and go beyond the limits of –A and +A.
 Derivation of Energy Levels
Schrodinger’s Equation for the Harmonic Oscillator

 2 2m
 ( E  U )  0 : Schrodinger’s Equation
x 2 h 2
1/ 2
1  2mv
y km  x x
d  2m 
2
1   h  h
2
 2  E  kx 2   0 (Ch. 5. 11)
dx h  2  2E m 2E
Substitution  
h k hv
in terms of α and y
d 2
2
 (  y 2 )  0
dy

* Condition to be normalizable : lim  0 
y  
|  |2 dy  1   2n  1

1
Energy levels of harmonic oscillator : En  (n  )hv
2
1
Zero point energy(n=0) : E0  hv
2

Wave Functions of Harmonic Oscillator

Hermite Polynomials
Choice of the parameter αn
A different wave function ψn


|  |2 dy  1 n  0,1,2...

Wave function : consist of a polynomial Hn(y)

→Hermite polynomial
The general formula for
1/ 4
the nth wave function :
 2mv   y2 / 2
n   n 1 / 2
 (2 n!) H n ( y )e
 h 

n Hn(y) αn En
1
0 1 1 2
hv
3
1 2y 3 2
hv

5
2 4y2-2 5 2
hv

7
3 8y3-12y 7 2
hv
9
4 16y4-48y2+12 9 2
hv
11
5 32y5-160y3+120y 11 2
hv
 Various Potential Wells
Various Potential Wells and Their Energy Levels

A hydrogen atom A particle in a box A harmonic oscillator

- The energy levels depend in a different way on the quantum number n.

- Only for the harmonic oscillator are the levels equally spaced.

Approximation of Harmonic Oscillator

The Greater the Quantum Number, The Closer Quantum Physics
Approaches Classical Physics

- When n = 0
Red line :
Probability densities for Exactly opposite behavior occurs
quantum mechanical when the quantum number is zero.
harmonic oscillator

White line : - When n = 10

Probability densities for
classical mechanical
harmonic oscillators |ψ|2 has approximately
general character of
the classical probability P.
Interpretation of QM (wavefunction)
The Copenhagen interpretation is an interpretation of quantum mechanics.
A key feature of quantum mechanics is that the state of every particle is
described by a wavefunction, which is a mathematical representation used to
calculate the probability for it to be found in a location or a state of motion.
According to this interpretation, the act of measurement causes the
calculated set of probabilities to "collapse" to the value defined by the
measurement. This feature of the mathematical representations is known as
wavefunction collapse. (By Bohr and Heisenberg in 1927)
Principles
– A system is completely described by a wave function ψ, which represents an
observer's knowledge of the system. (Heisenberg)
– The description of nature is essentially probabilistic. The probability of an
event is related to the square of the amplitude of the wave function related
to it. (Born rule, due to Max Born)
– Heisenberg's uncertainty principle states the fact that it is not possible to
know the values of all of the properties of the system at the same time; those
properties that are not known with precision must be described by
probabilities.
– Complementarity principle: matter exhibits a wave-particle duality. An
experiment can show the particle-like properties of matter, or wave-like
properties, but not both at the same time.(Niels Bohr)
– Measuring devices are essentially classical devices, and measure classical
properties such as position and momentum.
– The correspondence principle of Bohr and Heisenberg: the quantum
mechanical description of large systems should closely approximate the
classical description.

Paradoxes in QM
Schrödinger's Cat
– A cat is put in a box with a radioactive substance and a radiation detector
(such as a geiger counter). The half-life of the substance is the period of time
in which there is a 50% chance that a particle will be emitted (and detected).
The detector is activated for that period of time. If a particle is detected, a
poisonous gas will be released and the cat killed. Schrödinger set this up as
what he called a "ridiculous case" in which "The psi-function of the entire
system would express this by having in it the living and dead cat (pardon the
expression) mixed or smeared out in equal parts." He resisted an
interpretation "so naively accepting as valid a 'blurred model' for representing
reality." How can the cat be both alive and dead?
– The Copenhagen Interpretation: The wave function reflects our knowledge of
the system. The wave function simply means that there is a 50-50 chance that
the cat is alive or dead.

http://www.youtube.com/watch?v=HCOE__N6v4o&feature=related