3.

2 Consequences of Postulate 3
• An operator L with only one eigenvalue l and one eigenfunction y

eigenvalue equation

expectation value

expectation value = eigenvalue

 3.2 Consequences of Postulate 3
• An operator L with several eigenvalues l1, l2,..,ln and eigenfunctions y1,y2,..yn with the general
ansatz superposition principle (linear algebra)

eigenvalue equation

expectation value

eigenfunctions are orthogonal:

• cm2 is the probability that a quantum state m with eigenvalue lm can be occupied

• If all cm , except cmo , equal to zero: (expectation value = eigenvalue)

 3.2.1 Example 1: Plane Wave
Consider a wavefunction that has the form of a plane wave (frequency w, wavevector k):

Is this a plausible wavefunction?

à Infinite plane waves do not represent wavefunctions because they are not normalizable:

à Localized plane waves are normalizable and represent wavefunctions if they satisfy the
boundary conditions at x = a and x = b:

A wave of any shape can be constructed from a linear superposition of plane waves of different
frequencies and amplitudes (the essence of Fourier analysis)

à A plane wave is the building block of all wavefunction, from which waves of other
shapes (e.g. Gaussian-shaped waves) can be constructed
 3.2.2 Example 2: Probability Density /
Normalization
Consider the following functions:

( a ) y ( x, t ) = e (
i kx -wt )
(b) y ( x, t ) = sin( kx - wt ) (c) y ( x, t ) = sin( kx)

What is the meaning and difference?

( a ) y ( x, t ) = e (
i kx -wt )
w = E / ! k = + p / ! and y *y = 1
à A wave traveling to the right (positive momentum) + constant probability density

(b) y ( x, t ) = sin ( kx - wt ) w = E / ! k = + p / ! and y *y = sin 2 ( kx - wt )

à A wave traveling to the right (positive momentum) + non-constant probability density

(c) y ( x, t ) = sin ( kx ) = eiwt

2i
(
1 i( kx -wt ) i( - kx -wt )
e -e ) y *y = sin 2 ( kx )
à Superposition of wave traveling to the right and to the left: a standing wave + non-constant
probability density

Are the functions (a) and (b) normalizable?

à Generally not, only if they are confined in a finite space (e.g. potential well, exp. apparatus)
 3.2.3 Example 3: Position Operator
Consider the position operator x = x

- Eigenvalue equation: xˆ Y ( x, t ) = x Y ( x, t )
+¥ +¥
- Expectation value: xˆ = ò Y * ( x, t ) xˆ Y ( x, t )dx = ò Y * ( x, t ) x Y ( x, t )dx
-¥ -¥

Normalize y and calculate <x> and <x2> for the following wavefunctions:

Y ( x, t ) = e (
i kx -wt )
(a)

-l x
(b) Y ( x, t ) = Ae e - iwt with l , w , A positive real (use that Y(x,t) is symmetric in x;
problem 5 exercise sheet 4)
3.2.4 Example 4: Momentum & Energy Operator
Let us consider a wavefunction that has the form of a plane wave
i
- i (wt - kx ) - ( Et - px )
y ( x, t ) = y 0 e = y 0e !

The time and space derivations have the property:

d E d
Y ( x, t ) = -iwY ( x, t ) = -i Y ( x, t ) Þ i! Y = E Y
dt ! dt
d p ! d
Y ( x, t ) = ik Y ( x, t ) = i Y ( x, t ) Þ Y = pY
dx ! i dx

For such waves we can guess the energy operator E + momentum operator p with the
corresponding expectation values:

d +¥ d +¥ +¥
Hˆ = Eˆ = i! E = ò Y * Eˆ Ydx = ò Y *i! Ydx = ò Y * E Ydx = E
dt -¥ -¥ dt -¥

! d +¥ +¥
* ! d
+¥
pˆ = p = ò Y pˆ Ydx = ò Y
*
Ydx = ò Y * pYdx = p
i dx -¥ -¥ i dx -¥

The energy operator E is called Hamilton operator H

 3.3 Superposition Principle
• Postulate 4: The time-evolution of the wavefunction is governed by the TDSE, which is a
linear partial differential equation

à The superposition principle is valid (like for other linear differential equations, such as the
wave equation, the diffusion equation,…)

Superposition principle:
Let y1 and y2 be a solution of the TDSE
à Then any linear combination c1y1 + c2y2 is also a solution

à Any discrete or continuous linear combination of plane waves is a solution of the TDSE

Y linearcombination ( x, t ) = å i ci e
- i (wi t - ki x )
Y wavepackage ( x, t ) = ò j ( p)e - i( Et - px ) dp
 3.4 Complementary Functions
- Many physical phenomenon/ models (e.g. Bragg scattering, concept of the reciprocal
lattice) are easier to describe in momentum space (also k-space, wavenumber space)
f(k,t) instead of in position space y(x,t)

Fourier series/ transform

position space y(x,t) momentum space f(k,t)

- Mathematical view: The information contained in both representations (wave in position space &
wave in momentum space) seems to be equivalent

- Physical view: The uncertainty principle relating the uncertainty of the position of a wave packet
and the uncertainty of the wavenumber of a wave packet points to a complementary character of
wave in position space & wave in momentum space
 3.4.1 Fourier Transform
- Fourier transform is an operator (i. e. function) that has a function as an argument and is
assigned the value of the Fourier-transformed

momentum space

with wave number k which occurs as frequency in position space

à The Fourier-transformed gives the coefficients of decomposition

- The representation of the function via the Fourier-transformed is called inverse transform

position space

à The function can be represented by the coefficients + the basic functions eikx
 3.4.2 Example: Fourier Transform of a
Monochromatic Wave
- Consider a monochromatic wave (describes a particle that moves with constant velocity v in a
constant potential V(x)) æ æx öö
y mono ( x, t ) = y 0 sin ç 2p ç -n t ÷ ÷ = y 0 sin ( kx - wt )
è èl øø

- Linear wave equation à superposition principle is valid à polychromatic wave

¥ ¥
y ( x, t ) = å a n sin ( kn x - wnt ) = å A e( n
i kn x -wn t )
Fourier series for periodic functions kn = nk
n =1 n =-¥

1 ¥
or y ( x, t ) = ò A(k ) ei( kx -w ( k )t ) dk Fourier transform for non-periodic functions
2p -¥

- How to obtain the coefficients A(k) in the non-periodic case?

à It turns out that it is sufficient to calculate the amplitudes of y(x,t) at t = 0 (here w/o proof)
à y(x,0) is given: amplitude A is calculated via the Fourier transform

t=0

momentum space Delta function: d(k-q)

 3.4.3 Exact Uncertainty Relation - 1
- Consider a wave packet with a probability that has a gaussian distribution in position space
+ Fourier transform to momentum space
+ calculate the mean square fluctuation of the waves in position & momentum space

Due to divergence of the wave packet the calculation is only valid for t = 0

wave function: probability density:

x2 x2
1 - 2 1 - 2
position space
y ( x) = e 4 a2
such that y ( x) = e 2a
2p a 2p a

( Dx )
2 2 2
- Mean square fluctuation of position: = x- x = x2 - x
¥
- Expectation values: x = ò y * ( x) xy ( x) dx = 0 from anti-symmetry
-¥
¥
x 2 = ò y * ( x) x 2 y ( x) dx = a Gaussian integral
-¥

( Dx )
2 2
= x2 - x =a

- The Fourier-transformed wavefunction + probability distribution momentum space

1 ¥ 2a -( ak ) 2a -2( ak )2
ò
2 2
f (k ) = y ( x)e -ikx dx = ...calculation... = e f (k ) = e
2p -¥
2p 2p
 3.4.3 Exact Uncertainty Relation - 2
wave function: probability density:

2a -( ak ) 2 2a -2( ak )2
2
f (k ) = e f (k ) = e momentum space
2p 2p

( Dk )
2 2 2
- Mean square fluctuation of momentum: = k- k = k2 - k
¥
- Expectation values: k = ò f * (k ) k f (k ) dk = 0 from anti-symmetry
-¥
¥ 1
k 2 = ò f * ( x) k 2 f (k ) dk = Gaussian integral
-¥ 4a 2
1
( Dk )
2 2
= k2 - k =
2a
- The mean square fluctuations fulfill the following relation:
1 1
( Dx ) ( Dk )
2 2
= =a
2a 2
- With the de Broglie relation p = !k

! This is the exact uncertainty relation for complementary waves

( Dx ) ( Dp )
2 2
=
2 à refinement of the previous consideration
 3.5 Vector Spaces with Functions as Vectors
Function vector space:

- Functions can be considered as vectors if their function values are real or complex numbers

- The vector addition is defined by a function that returns the sum of the values of both functions

- Examples: continuous/ differentiable functions over an interval [a, b], square integrable functions
over an interval [-µ,µ]
- A scalar product between two functions y1 and y2 over an interval [a, b] can be defined by an
b
integration y 1 ×y 2 = y 1 ,y 2 = ò y 1* ( x)y 2 ( x)dx
a
à such an integral is only finite if the functions y1 and y2 are square integrable
b
y 1 ,y 12 = ò y 1* ( x)y 1 ( x)dx < ¥
a
à i. e. the function must be normalizable
- In (complete) function vector spaces, bases can be defined (e. g. polynomials, sin/ cos functions)
à With a base bn (n = 1 ,2 ,..) an arbitrary vector a can be written as a linear span

a = Sn cn bn
- The superposition principle requires that the physical quantities are elements of a vector space
à Quantities are solutions from a physical law with a linear equation (e. g. wave equation)
 3.6 Mathematics for Quantum Mechanics - 1
Vector spaces V are sets with an operation “+” (vector addition) with properties, a, b, c Î V:
• Commutativity: a + b = b + a
• Associativity: a + ( b + c ) = ( a + b ) + c Abelian
group
• Inverse element: for each a Î V exists –a with a + (-a) = 0

Scalar multiplication, a, b, c Î V, a ,b, g Î real or complex number: vector

• Distributive law: a (a + b) = a a + a b and ( b + g )a = b a + g a space
• Unity scalar: $ 1 1a=a

Scalar product, a, b, c Î V, a, b, g Î real or complex number:

• Scalar product between two vectors: a×b = b×a = Î real or complex Hilbert
space
• Semilinear: a×(a b) = a a×b (aa)×b = a* a×b
• Unity scalar: $ 1 1a=a

- Vector spaces with a scalar product are pre-Hilbert spaces

- The scalar product defines a norm with |a| = sqrt(a×a)

- A Hilbert space V is a pre-Hilbert space which is complete

(i. e. each Cauchy sequences converges in V)
 3.6 Mathematics for Quantum Mechanics - 2

Orthonormal basis:
• Two vectors a,b Î V are orthogonal if a×b = 0
• A vector is normalized if a×a = 1
• A sequence of vectors ai Î V is a basis if the linear span Siaiai covers the whole V
• A sequence ai Î V is an orthonormal basis (ONB) if it is a basis + if ai×bj = dij
(Kronecker symbol d)
3.7.1 Example: System in an Eigenstate / a Qubit
- Eigenstate 1: wavefunction Y1(q1), eigenvalue E1
considered system
- Eigenstate 2: wavefunction Y2(q2), eigenvalue E2

1. System in pure state 1 (or 2): the expectation value is identical to an eigenvalue l1 (or l2)

2. Wave function for a system where the two states are completely independent from each other
(from separation of Schrödinger equation)

3. Coherent superposition of Y1 and Y2 as linear combination with c1, c2 ÎC yields a pure state

from linearity of Schrödinger equation

à Each measurement has either with probability c12 the result 1 with eigenvalue E1 or with
probability c22 the result 2 with eigenvalue E2
here the expectation value is not equal to an eigenvalue

A system which is a coherent superposition of two states is nowadays called a “qubit” and
is the basis for quantum computing
3.7.2 Other Description of Quantum States
Beside pure states & completely uncorrelated states, there are other states + mathematical
formalisms, which we do not discuss here

Mixed states which are described by the density matrix instead of the wavefunction
• Such systems can be partially coherent + partially incoherent (entangled systems)
• The discussion of paradoxical properties is usually done using the density matrix approach

Particle density instead of wavefunction as the elementary quantity to describe systems

à Basis of density functional theory
• All useful calculations nowadays are done with density functional theory
• The Schrödinger equation is essentially unsolvable (for nontrivial systems)
 3.7.3 Commutator - 1
In General, the order of the operators has to be strictly maintained. The reason for this is that
most operators do not commute

à If 2 operators commute, it is always possible to find functions which are eigenfunctions of

both operators
let
two operators that
and commute are called
compatible
then

à The eigenfunctions of B are also the eigenfunctions of A and differ by only a scalar k
 3.7.3 Commutator - 2
à If 2 operators do not commute, there is no set of eigenfunctions, which are eigenfunctions
of both operators

à In an experiment, the observed quantities are not simultaneously sharp defined

à Non commuting operators are, e. g. x and

à Position x and momentum px are not both simultaneously sharp defined

two operators that not

commute are called
incompatible

gives rise to the

uncertainty principle