Principles of quantum mechanics

Wave-particle duality
Particle properties of waves
Wave properties of particles
Wave-particle duality: particles vs. waves

• A particle is a localized point-like object with well-defined position and velocity, and
also energy and momentum.

More precisely: a particle is an object whose linear dimensions are negligible on the
length-scale of a given problem at hand.

A free particles moves with a constant velocity from some initial position:
  
r  v t  r0

• A wave is a delocalized time-dependent perturbation which is distributed in space.

Examples:

– pressure and density perturbations in the sound wave;

– waves on a string;
– water level perturbations on the ocean;
– electric and magnetic fields in an electromagnetic wave.
Wave-particle duality: particles vs. waves

• A plane wave is described by a “wave function” proportional to

 
sin(k x x  k y y  k z z  t )  sin(k  r  t )
• 
Note that the wave function above is periodic both in time and in space in the
direction of the wave vector k

2
• Space period = wavelength =   
|k |
2
• Time period = T 

• Wave speed = phase velocity = speed of propagation
 ofits peak:
      k k
k r  t  const  r  v t  r0 , v   2
T |k | k
• Physics before the 20th century: waves and particles are fundamentally different

• Wave-particle duality (early 20th century and on): all particles have wave properties
and vice versa!
Wave-particle duality: particle properties of waves

• Thermal radiation law (Max Planck, 1900): light propagates in discrete chunks of
energy, or quanta, called photons. Each photon moves with the speed of light and
carries the energy proportional to its frequency: E  hf  
h  6.6260704 ... 10 34 J  s  4.13566766 ... 10 15 eV  s
Planck’s constant:
  1.0545718 ... 10 34 J  s  6.58211951 ... 10 16 eV  s
• Photoelectric effect (Albert Einstein, 1905): light-induced emission of electrons by
metal surfaces

EK h w
E K  hf  w  VS   f 
e e e
• Scattering of x-rays (light of very short wavelength) by matter (Arthur Compton, 1923)
indicates that light particles also carry momentum h
p

Wave-particle duality: wave properties of particles

• De Broglie’s hypothesis (1924): a particle is also a wave with the

h
de Broglie’s wavelength: 
p

• In terms of kinetic energy:

p2 h
EK   p  2mEK  
2m 2mE K
• Experimental confirmation: Davisson-Germer experiment (1925)
Electron of energy 50 eV has the wavelength ca. 1.7 Å, which is comparable to the
lattice constant. Hence, can observe electron diffraction on a crystal, which acts as a
diffraction grating.
De Broglie wavelength: sample problems

Find a numerical relation between de Broglie wavelength (in Å) and energy (in eV) for
(a) a free electron (me = 9.11·10-31 kg),
(b) a proton (mp = 1836 me),
(c) a photon.
De Broglie wavelength: sample problems

A photon with wavelength 300 nm kicks an electron out of a metal with the work function
w = 3.5 eV. Determine de Broglie wavelength of this electron.
Principles of quantum mechanics

De Broglie’s wavelength and

energy quantization
The wave function
De Broglie wavelength: sample problems
h
De Broglie wavelength is related to the particle’s momentum as λ = , regardless if
p
the particle has a mass (e.g. electron) or does not (e.g. photon). The energy of a

photon is E ph = h f . Is this energy expression true also for electrons?

De Broglie wavelength and energy quantization
h
• Main results from last lecture: λ = for all particles and waves
p
−34
Planck’s constant: h ≅ 6.626 ⋅ 10 J ⋅ s

• A particle between two walls is a

standing wave with nodes on the walls:

• A particle moving on a circle is a traveling wave that repeats itself after making one
full circle:
De Broglie wavelength and energy quantization

• Example 1: Find the possible energies of a particle between two walls

h nh
d = nλ / 2 p= =
λ 2d

p2 h2
E= =n 2

2m 8md 2

• Example 2: Find the possible energies of a particle on a ring

h nh
2π r = nλ p= =
λ 2π r

p2 h2
E= =n 2

2m 8π 2 r 2m
Energy quantization: sample problem

Find the energies of an electron in a hydrogen atom, assuming the proton to be

stationary. What are the possible radii of the electron’s orbit?
Principles of quantum mechanics

Wave function
Energy and momentum operators
Time-dependent Schrödinger’s equation
Time-independent Schrödinger’s equation
The wave function

• De Broglie wavelength expression λ = h / p is of limited use, because it is true for

a free particle only. What do we do if a particle is in a potential?

• A more general approach is based on the concept of a wave function ψ ( r , t ) . It is
complex-valued:
    
iθ ( r ,t )
ψ ( r , t ) = Reψ ( r , t ) + i Imψ ( r , t ) = ψ ( r , t ) e , i 2 = −1

• The phase θ ( r , t ) is unmeasurable, but its space and time derivatives are.

• Physical meaning: The probability to find the particle in a small volume dV around a
  2
(
point r at time t is: dV ψ ( r , t ) = dV (Reψ ) + (Imψ ) = dV ψψ
2 2 ∗
)

ψ (r , t )
2
i.e. is probability density.

• Normalization of the wave function: Consider a particle in a finite volume V .

Then the total probability must be 1:  2
∫ dV ψ (r , t )
V
=1
Remarks

• For a particle in 3 dimensions: probability to find the particle in dx dy dz is

|ψ ( x, y , z, t ) |2 dx dy dz

• For a particle in 2 dimensions: probability to find the particle in dx dy is

|ψ ( x, y , t ) |2 dx dy

• For a particle in 1 dimension: probability to find the particle in dx is

|ψ ( x, t ) |2 dx

• Euler’s formula: ei θ = cos θ + i sin θ for any real-valued θ

• An oscillatory process: cos(ω t ) = Re eiω t , sin(ω t ) = Im eiω t

  iωt
• We will care about the stationary states, for which ψ ( r , t ) = Ψ ( r ) e
 2 2 
and thus |ψ ( r , t ) | = Ψ ( r )

• For more info about complex variables: see the end of part 1.1 of the Lecture Notes
The wave function: sample problem

• A particle’s wave function depends on the x - coordinate only:

ψ ( x, t ) = A x e − k |x| eiω t
with k = 0.2 Å-1. At what positions x is the particle most likely and least likely to be
found? What is the normalization constant A?
The wave function of a free particle

( )
 
i ( k r −ωt )
 
• Plane wave: ψ ( r , t ) = Ae = A cos(k r − ωt ) + i sin(k r − ωt )
 2
• Probability density of a free particle : ψ ( r , t ) = A2 is constant everywhere

• Standard normalization: The particle finds itself in a very large cube of size L whose
edges are oriented along the coordinate axes. Then

 2 1  1 
∫V ψ = = ⇒ = ψ r −ωt )
2 3
dV ( r , t ) A L 1 A , i.e. ( r , t ) = e i ( k
L3 / 2 L3 / 2
• Periodic boundary conditions (recall particle on a ring):
      
ψ ( r + Le x , t ) = ψ ( r + Le y , t ) = ψ ( r + Le z , t ) = ψ ( r , t )
 2π 
This means that L = nx λx = n y λ y = nz λz and k= n
L
Principles of quantum mechanics

Hydrogen quantum numbers

Degeneracy
Spin
Indistinguishability of quantum particles
Spin-statistics theorem
Time-independent Schrödinger’s equation (TISE)
  − iEt / 
• In a stationary state ψ ( r , t ) = Ψ ( r )e
 2  2 
• Time-independent Schrodinger’s equation: EΨ ( r ) = − ∇ Ψ + V ( r )Ψ
2m
2 ∂ 2Ψ ∂ 2Ψ ∂ 2Ψ
• Laplacian in 3 dimensions: ∇ Ψ= 2 + 2 + 2
∂x ∂y ∂z
2 ∂ 2Ψ ∂ 2Ψ
in 2 dimensions: ∇ Ψ= 2 + 2
∂x ∂y
2 ∂ 2Ψ
in 1 dimension: ∇ Ψ= 2
∂x
• Solution of this equation with the appropriate boundary conditions yields the possible
energies Eα and the corresponding stationary wave functions, Ψα. They depend on
a set of quantum numbers
α = (α1, α2, …), which define the specific quantum state of the system.
TISE sample problem

Use the TISE to find the allowed energies and wave functions of a particle of mass m
performing one-dimensional motion inside a box of side length d.
Hydrogen quantum numbers
 2  2 
• Time-independent Schrödinger equation EΨ ( r ) = − ∇ Ψ + V ( r )Ψ
2me
 e2
with V ( r ) = − kC can be solved exactly
r
• The solution, Ψα, turns out to depend on three quantum numbers, i.e.:
α = ( n, l , m )
Ry
• Principal quantum number n = 1, 2, 3, …: determines the energy En = −
n2
• Orbital quantum number l = 0, …, n –1: determines the magnitude of the angular
momentum
L =  l (l + 1)
• Magnetic quantum number m = –l, …, l : determines the projection of the angular
momentum on some selected axis, say, the z-axis

Lz = m
Spin

• An electron also possesses its own angular momentum, which is not related to its
orbital motion. This internal angular momentum of an electron is called “spin”.

• An electron is a spin-½ particle. Its angular momentum projection on some selected

axis can have only two values:

1
S z = s , s=±
2

• A quantum state of an electron in hydrogen atom is defined by 4 quantum numbers:

(n, l, m, s). The energy
Ry
Enlms =− 2
n
independent of l = 0, …, n –1, m = –l, …, l , and s = – ½ , ½.
Degeneracy

• The situation when more than quantum state have the same energy is referred to as
degeneracy.

• The number of different states corresponding to a particular energy level is known as

the degree of degeneracy, or simply degeneracy, of that level. Denote degeneracy
with the letter g.

• Degeneracy of the nth energy level of hydrogen: gn = 2n2.

The factor of 2 comes from two possible spin orientations.

The n2 term comes from the number of possible values that the quantum numbers
number l = 0, …, n –1: and number m = –l, …, l can have:
n −1 l n −1 n −1 n −1
( n − 1)n
∑ ∑ 1
l =0 m = − l
= ∑
l =0
( 2 l + 1) = 2 ∑
l =0
l + ∑
l =0
1 = 2
2
+ n = n 2
Degeneracy: sample problem 1

Eigenstates of an isotropic two-dimensional simple harmonic oscillator of mass m and

spring constant k depend on 2 quantum numbers, n1 and n2, which can take on values 0,
1, 2, 3, … . The energy is

E ( n1 , n2 ) = ω ( n1 + n2 + 1)
with the natural frequency ω = k / m . Find the degeneracy of the nth energy level
with energy En = ω ( n + 1)
Degeneracy: sample problem 2

Eigenstates of an isotropic three-dimensional simple harmonic oscillator of mass m and

spring constant k depend on 3 quantum numbers, n1, n2, n3, with eigenenergies

E n = ω ( n + 3 / 2 ) n = n1 + n2 + n3
Find degeneracy of nth energy level.
Indistinguishability of quantum particles

• In quantum physics, the concept of trajectory is meaningless.

• Impossibility to follow the motion of each particle implies impossibility to label

particles, i.e. to distinguish particles from each other.

• The quantum state of a system containing 2 particles is described by a 2-particle

wave function  
Ψ ( r1 , r2 )
If we interchange the arguments of the wave function, we will obtain a physically
equivalent wave function
 
Ψ ( r2 , r1 )

• But the wave function is unmeasurable, only its modulus is. Then
   
| Ψ ( r1 , r2 ) | = | Ψ ( r2 , r1 ) |
Spin-statistics theorem

• The wave function is unmeasurable, only its modulus is. Then, for two particles
   
Ψ ( r1 , r2 ) = c Ψ ( r2 , r1 ) , | c |= 1
• To find the constant c, perform another interchange:
     
Ψ ( r1 , r2 ) = cΨ ( r2 , r1 ) = c Ψ ( r1 , r2 )
2

• Thus c 2 = 1 ⇒ c = ±1
• Spin-statistics theorem (W. Pauli, 1940): Particles with integer spin (0, 1, 2, …) have
the two-particle wave function which remains the same if any the coordinates are
interchanged; such particles are called bosons.

Particles with half-integer spin (1/2, 3/2, 5/2, …) have the two-particle wave function
which changes sign if any two coordinates are interchanged; such particles are
called fermions.

• Bosons: photons, gravitons, Higgs, etc.

Fermions: electrons, protons, neutrons, etc.
Pauli exclusion principle

• Denote a single-fermion wave function in a state α as Ψα (r )

• A two-fermion wave function can be written as an antisymmetrized product of two

one-particle wave functions

 
Ψαβ ( r1 , r2 ) =
1
(Ψα (r1 )Ψβ (r2 ) − Ψα (r2 )Ψβ (r1 )) = −Ψαβ (r2 , r1 )
     
2

• If states α and β are the same, then

     
Ψαα ( r1 , r2 ) =
1
(Ψα ( r1 )Ψα ( r2 ) − Ψα ( r2 )Ψα ( r1 ) ) = 0
2
which means that two fermions cannot occupy the same quantum state.