I incident II

reflected transmitted

 2
2
i   x, t      x, t   V  x, t    x, t  En   n  12  
t 2m x 2
Heisenberg realized that ...
 In the world of very small particles, one cannot measure any
property of a particle without interacting with it in some way
 This introduces an unavoidable uncertainty into the result
 One can never measure all the
properties exactly
 It does not observe the effects of
the uncertainty principle in
everyday life

Werner Heisenberg (1901-1976)

Image in the Public Domain
Our Course outline today
 Wave Function for a Free Particle
 1D Wave equation
 3D Wave equation
 Physical Interpretation of the wave function
 An equation for matter waves?
 De Broglie postulated that every particles has an associated wave of
wavelength:
  h/ p
 Wave nature of matter confirmed by electron diffraction studies etc (see
earlier).
 If matter has wave-like properties then there must be a mathematical
function that is the solution to a differential equation that describes
electrons, atoms and molecules.
 The differential equation is called the Schrödinger equation and its
solution is called the wavefunction, .
 What is the form of the Schrödinger equation ?
 Heisenberg’s Matrix Mechanics
1924: de Broglie suggests particles are waves
Mid-1925: Werner Heisenberg introduces Matrix Mechanics
•Semi-philosophical, it only considers observable quantities
•It used matrices, which were not that familiar at the time
•It refused to discuss what happens between measurements
•In 1927 he derives uncertainty principles
Late 1925: Erwin Schrödinger proposes wave mechanics
•Used waves, more familiar to scientists at the time
•Initially, Heisenberg’s and Schrödinger’s formulations were competing
•Eventually, Schrödinger showed they were equivalent; different descriptions which
produced the same predictions
Both formulations are used today, but Schrödinger is easier to understand
 The Free Schrödinger Equation
1925: Erwin Schrödinger proposes wave mechanics
•Peter Debye suggested to him he needed to find a wave equation
for quantum mechanics
•He hit on the idea of using complex waves p2
E
•The rest is history   x, t  2m
•Starting point: Energy/Momentum relationship p2
•Multiply by the wave function on the right E   x, t     x, t 
•Use de Broglie relations to rewrite 2m
i i 
E  p k   x, t   exp  ikx  it   exp  px x  Et 
 
•Use relationships for complex waves to rewrite with derivatives
 i 
 p p  i  2
2
x x i   x, t      x, t 
 i  t 2m x 2

 E E i
t t
 The Schrödinger Equation
The General Prescription for Classical  Quantum:
1. Write a formula for the energy in terms of momentum and position
2. Transform Energy and momentum using the following prescription:
 
E   i p  k  i
t
3. Rewrite it as a wave equation
x
What if we have forces?
•Need to add potential energy V(x,t) on top of kinetic energy term
2  2
2
E
p
V  x, t  i   V  x, t 
2m t 2m x 2

 2
2
i   x, t      x, t   V  x, t    x, t 
t 2m x 2

 2
2
i  V 
t 2m x 2
The Time-Dependent Schrödinger Equation
TDSE
p2
E  V ( x, t )
 For a particle in a potential V (x,t) then 2m
 and we have (Total energy)  wavefunction = (T+ V)  wavefunction
 2
2
i   V ( x, t ) TDSE 
Points of note: t 2m x 2

1. The TDSE is one of the postulates of quantum mechanics. Though the SE cannot be
derived, it has been shown to be consistent with all experiments.
2. SE is first order with respect to time (see: classical wave equation).
3. SE involves the complex number i and so its solutions are essentially complex. This is
different from classical waves where complex numbers are used imply for convenience –
see later.
 The Superposition Principle
 2
2
3. This equation is linear i   x, t      x, t   V  x, t    x, t 
•The wave function t 2m x 2

appears to the first power everywhere Let 1 and 2 be two solutions

•You can take linear combinations of solutions: of Schrödinger. Then so is
  x, t   c11  x, t   c2  2  x, t 
  x, t  1  x, t   2  x, t  where c1 and c2 are arbitrary
i  c1i  c2i
t t t complex numbers
 2
 2  1  x, t    2
 2  2  x, t  
 c1    V  x, t  1  x, t    c2    V  x, t   2  x, t  
 2m x 2
  2m x 2

2
2
2  1 1
 c  x, t   c2  2  x, t    V  x, t  c11  x, t   c2  2  x, t  
2m x
2
 2   x, t 
  V  x, t    x , t  Q.E.D
2m x 2
The Hamiltonian operator
 2  2  2 2 
 TDSE can be written as:  
 V ( x, t )      V ( x, t )   Hˆ 
2m x 2
 2m x
2


 where Ĥ is called the Hamiltonian operator which is the differential

operator that represents the total energy of the particle.
 Thus  2 2  pˆ 2
Hˆ     V ( x )  
 2m
x
 Vˆ ( x)
 2 m x 2



 where the momentum operator is pˆ x  i
x

ˆ 
 Thus shorthand for TDSE is: H  i
t
 Solve TDSE to be Time Independent problems
 2
2
•Often [usually] the i   x, t      x, t   V  x    x, t 
potential does not t 2m x 2

•To solve this equation, we try separation of variable: 

 x, t     t   x 
depend on time: V = V(x).

•Plug this guess in:  2

 2

•Divide by the i   x   t      t  2   x  V  x    t   x 
t 2m x
original wave function
•Note that left side is independent of x, and right side is independent of t.
•Both sides must be independent of both x and t
•Both sides must be equal to a constant, called E (the energy)

i d  t  2
d 2  x 
 V  x  E
  t  dt 2m  x  dx 2
 Solving the time equation   x, t     t   x 
i d  t 
E
  t  dt
•We have turned one equation into two
•But the two equations are now ordinary differential equations
•Furthermore, the first equation is easy to solve:
d  t  Edt d iE iEt
    dt ln   t      t   eiEt
 t  i 
•These types of solutions are called stationary states
•Why? Don’t they have time in them?
  x, t   e iEt   x 
•The probability density is independent of time

  x, t   e   x e  * x    x
2  iEt iEt 2
The Time Independent Schrödinger Eqn TISE
2
d 2  x  2
d 2  x 
E V  x E  x     V  x   x 
2m  x  dx 2
2m dx 2

Multiply by (x) again 2

d 2

•This equation is much easier to solve than the E   2
 V
original equation 2m dx
•ODE’s are easier than PDE’s
•It can pretty easily be solved numerically, if necessary
•Note that it is a real equation – you don’t need complex numbers
•Imagine finding all possible solutions n(x) with energy En
•Then we can find solutions of the original Schrödinger Equation
  x, t    n  x  exp   iEnt 
•The most general solution is superposition of this solution

  x, t    cn n  x  exp   iEnt 

n
Stationary states
 er in the lecture we saw that even when the potential is independent of
time the wavefunction still oscillates in time:
 Solution to the full TDSE is:
 ( x, t )   ( x) T (t )   ( x)e iEt / 

 But probability distribution is static:

P( x, t )   ( x, t )   * ( x)e  iEt /   ( x)e iEt /    ( x)
2 2

 Thus a solution of the TISE is known as a Stationary State.

 Interpretation of (x,t)
 As mentioned previously the TDSE has solutions that are inherently complex  (x,t)
cannot be a physical wave (e.g. electromagnetic waves). Therefore how can  (x,t)
relate to real physical measurements on a system?
 The Born Interpretation
Probability of finding a particle in a small length dx at position x and time t is equal to

2
 ( x, t ) ( x, t )dx   ( x, t ) dx  P( x, t )dx
*

 * is real as required for a probability distribution and is the probability per unit
length (or volume in 3d).
 The Born interpretation therefore calls  the probability amplitude,
* (= P(x,t) ) the probability density
* dx the probability.
Expectation values
 Thus if we know (x, t) (a solution of TDSE), then knowledge of
* dx allows the average position to be calculated:

x   xi P( xi ) x
i
 In the limit that x 0 then the summation becomes:
 

 
2
x x  xP( x)dx  x ( x, t ) dx
 
 The average is also know as the expectation value and are very
important in quantum mechanics as they provide us with the average
values of physical properties because in many cases precise values
cannot, even in principle, be determined – see later.
 
 Similarly
 x P( x)dx   x
2
x 2
 2 2
( x, t ) dx
 
 Normalisation
 Total probability of finding a particle anywhere must be 1:
 

 
2
P( x)dx  ( x, t ) dx  1
 

 This requirement is known as the Normalisation condition. (This condition

arises because the SE is linear in  and therefore if  is a solution of TDSE
then so is c where c is a constant.)
 Hence if original unnormalised wavefunction is (x,t), then the
normalisation integral is: 


2
N2   ( x, t ) dx

 And the (re-scaled) normalised wavefunction norm = (1/N) 
 Example 1: What value of N normalises the function x (x  L) of 0  x  L?
 Example 2: Find the probability that a system described by the function
21/2sin (x) where 0  x  1 is found anywhere in the interval 0  x  0.25.
Boundary conditions for 
 In order for  to be a solution of the Schrödinger equation to represent
a physically observable system,  must satisfy certain constraints:
1. Must be a single-valued function of x and t;
2. Must be normalisable; This implies that the   0 as x  ;
3.  (x) must be a continuous function of x;
4. The slope of  must be continuous, specifically d (x)/dx must be
continuous (except at points where potential is infinite).

(x) (x) (x) (x)

x x x x
 What other information can you get from ? (and
how!)
 We have seen how we can use the probability distribution  to calculate the
average position of a particle. What happens if we want to calculate the average
energy or momentum because they are represented by the following differential
operators:

 2 d2  
Hˆ    V ( x) pˆ x  .
2m dx 2
i x
 Do the operators work on , or on , or on  alone?
 Take TISE and multiply from left by  and integrate:
Hˆ  n  En n

  Hˆ  dx    E  dx  E   dx  E NB  is normalised.
n n  n n n n  n n n

Suggest that in order to calculate the average

ˆ  dx
 
value of the physical quantity associated with the n n
QM operator we carry out the following
integration:
 Momentum and energy expectation values
 The expectation value of momentum involves the representation of
momentum as a quantum mechanical operator:

   

p x   * ( x, t )

i x
( x, t )dx ˆ
p x 
i x
.

 is the operator for the x component of momentum.

 Example: Derive an expression for the average energy of a free particle.
p2 p2
E E 
2m
 Since V = 0 the expectation value for energy for a particle2m
moving in one
dimension is 
 2 2 
E    * ( x, t )  2m x

2
 ( x, t )dx


 Our definition of the expectation value is one of the postulates of QM –
see later lectures.
 Today’s Culture Moment
Schrödinger's cat
“It is typical of these cases that an indeterminacy
originally restricted to the atomic domain
becomes transformed into macroscopic
indeterminacy, which can then be resolved by
direct observation. That prevents us from so
naively accepting as valid a "blurred model" for
representing reality. In itself, it would not
embody anything unclear or contradictory. There
is a difference between a shaky or out-of-focus
photograph and a snapshot of clouds and fog
banks.”

-Erwin Schrodinger, 1935

Solvay Conference
Copenhagen Interpretation of Quantum
Mechanics

 A system is completely described by a wave function ψ, representing an observer's subjective

knowledge of the system.
 The description of nature is essentially probabilistic, with the probability of an event related to the
square of the amplitude of the wave function related to it.
 It is not possible to know the value of all the properties of the system at the same time; those
properties that are not known with precision must be described by probabilities. (Heisenberg's
uncertainty principle)
 Matter exhibits a wave–particle duality. An experiment can show the particle-like properties of matter,
or the wave-like properties; in some experiments both of these complementary viewpoints must be
invoked to explain the results.
 Measuring devices are essentially classical devices, and measure only classical properties such as
position and momentum.
 The quantum mechanical description of large systems will closely approximate the classical
description.