“‘Quantum mechanics’ is the description

of the behavior of matter and light in all

its details and, in particular, of the
happenings on an atomic scale. Things on
a very small scale behave like nothing
that you have any direct experience
about. They do not behave like waves,
they do not behave like particles, they do
not behave like clouds, or billiard balls, or
weights on springs, or like anything that
you have ever seen.”
--Richard P. Feynman
 Lecture 07: Introduction to
Quantum Physics:-Matter Waves and
the
Schrödinger Equation
 Content

De Broglie’s hypothesis of particle-wave duality

Matter-wave Interference

Composite particles
 Electron microscopy

 Heisenberg Uncertainty Principle

 Schrödinger Equation (SEQ)
 Time-independent SEQ gives static solutions for wavefunctions
 Physical interpretation of the wavefunction
De Broglie’s hypothesis of particle-wave duality
electron
gun

DeBroglie (1924) proposed that, like detector
photons, particles have a wavelength:
Inversely proportional to 
= h/p momentum.


In 1927-8, it was shown (Davisson-Germer) that, like x-rays, ELECTRONS can also
diffract off crystals !

Ni Crystal


Interference peak !

Electrons can act like waves!!

I()
• We will see later that the discrete atomic emission lines also arise from the
wavelike properties of the electrons in the field of the nucleus:

o
0 60


What does this mean? 
Atomic In discussion section:
hydrogen
 “Double-slit” Experiment for Electrons
 Electrons are accelerated to
50 keV   = 0.0055 nm
 Central wire is positively
charged  bends electron
paths so they overlap
 A position-sensitive detector
records where they appear.
 << 1 electron in system at
any time

[A. TONOMURA (Hitachi) --

pioneered electron holography]

Exposure time: 1 s 10 s 5 min 20 min

 Exercise 1: Matter wavelengths

What size wavelengths are we talking about? Consider a photon with energy 3 eV, and therefore momentum p = 3 eV/c. Its
wavelength is:

h 4 .14  10 15 eV  s
 
p 3 eV
 
 c  1.4  10 15 s  3  108 m / s  414 nm 
 What is the wavelength of an electron with the same momentum?

a) e = p b) e < p c) e > p
 Exrcise 1: Matter wavelengths

What size wavelengths are we talking about? Consider a photon with energy 3 eV, and therefore momentum p = 3 eV/c. Its
wavelength is:

h 4.14  10 15 eV  s
 
p 3 eV
 
 c  1.4  10 15 s  3  108 m / s  414 nm 
 What is the wavelength of an electron with the same momentum?

a) e = p b) e < p c) e > p

e = h/pe Same relation for

particles and photons.

 Note that the kinetic energy of the electron is different from the
energy of the photon with the same momentum (and wavelength):

KE 
p 2

h

2
6.625  10 J s  34
 1 . 41 
2
10  24
J
2 m 2m 2  31  9 2
2( 9.11 10 kg )( 414  10 m )
 1.602  1019 J / eV  8.8  10 6 eV
Compared to the energy of the photon (given above): E  pc  3 eV
 Wavelength of an Electron or other
particles

The DeBroglie wavelength of an electron is inversely related
to the electron momentum:
= h/p
 Frequently we need to know the relation between the
electron’s wavelength  and its kinetic energy E.
p and E are related through the classical formula:
p2
E m e  9.11  10 -31kg
2m
h2 always
p = h/ E h  4.14  10 -15eV  s
2m 2 true!
In addition (with approximation):
•Energy (kinetic) of particles: E=1/2 mv2
•Momentum of particles: p=mv
 Interference of larger particles
 Matter-wave interference has now been demonstrated with electrons,
neutrons, atoms, small molecules, BIG molecules, & biological molecules

Recent Example: Interference of C60, a.k.a. “fullerenes”, “buckyballs”
Mass = (60 C)(12 g/mole) = 1.2 x 10-24 kg
p2 3
 K .E .  kT  p  3kTm  2.1  10  22 kg m / s
2m 2
 = h/p = 2.9 pm (c.f. C60 is ~ 1 nm across!)

[A. Zeilinger (U. Vienna), 1999]

 Application of Matter Waves:
Electron Microscopy
 The ability to “resolve” tiny objects improves as the wavelength
decreases. Consider the microscope objective:
Objects to D
d
be resolved 

diffraction
f disks
= focal length of lens if image (not interference
plane is at a large distance. maxima)

Critical angle for  The minimum d for which we f

resolution:  c  1 . 22 can still resolve two objects d min  f c  1.22
D is c times the focal length: D

A good microscope objective has f/D  2, so with  ~ 500 nm

the optical microscope has a resolution of dmin  1 m.

We can do much better with matter waves because, as we shall see,

electrons with energies of a few keV have wavelengths less than 1 nm.
The instrument is known as an “electron microscope”.
 Application of Matter Waves:
Electron Microscopy

Scientists and engineers - such as those here at the Materials Research

Lab and the Beckman Institute - use “electron microscopy” to study
nanometer-scale structures in materials and biological systems

Cu “islands” Compound eye

in a Cu film of a fly

(//ntweb.mrl.uiuc.edu/cmm/) (//www.itg.uiuc.edu/)
 Example: Imaging a Virus*
 Electron Microscopy of a Virus: electron gun

You wish to observe a virus with a diameter of 20 nm, Electron

optics
which is much too small to observe with an optical D

microscope. Calculate the voltage required to produce an

electron DeBroglie wavelength suitable for studying this f

virus with a resolution of dmin = 2 nm. The “f-number”

for an electron microscope is quite large: f/D  100.
(Hint: First find required to achieve dmin with the given f/D. object

Then find E of an electron from .)

Answer: 5.6 kV
 Solution
 Electron Microscopy of a Virus: electron gun

You wish to observe a virus with a diameter of 20 nm, Electron

optics
which is much too small to observe with an optical D

microscope. Calculate the voltage required to produce an

electron DeBroglie wavelength suitable for studying this f

virus with a resolution of dmin = 2 nm. The “f-number”

for an electron microscope is quite large: f/D  100.
(Hint: First find required to achieve dmin with the given f/D. object

Then find E of an electron from .)

f
d min  1.22
D
 D   D 
  d min    2 nm   0.0164 nm
 1.22 f   1.22 f 

h2 1.505 eV  nm 2
E 2
 2
 5 .6 keV
2m 0.0164 nm 
To accelerate an electron to an energy of 5.6 keV requires 5.6
kilovolts . (The beauty of electron-volt units)
Summary: Photons, Matter Waves

Light
• p = h/ (matter also)
• p = E/c
• E = hf = hc/

Matter
• p = h/(light also)
• p  2 mE
• E = h2/2m2

Heisenberg Uncertainty Principle
So, particles (electrons, photons, etc.) also have wave-like properties – reflect a fundamental uncertainty in our ability to precisely “know” the particle’s location.

It is well known in classical waves that one can produce a localized “wave packet” by superposing waves with a range of wave vectors k. We can imagine such a packet in space:


Fourier analysis shows that: k·x  1.

Interpretation: To make a short wavepacket requires a broad spread in wavelengths. Conversely, a single-wavelength wave extends forever.

From the quantum relation between momentum and wave vector (p = hk), there is always a trade-off between how well one can measure a particle’s location x (particle-like) and momentum p (wave-like):
ħ (k·x  1)  (ħk)·x  ħ  px ·x  ħ
This relation is known as the Heisenberg Uncertainty Principle.

x
 Heisenberg Uncertainty Principle: Example
Consider an electron in the lowest-energy state of a hydrogen
atom; its position is known to an accuracy of about 0.05 nm (the
radius of the atom). How well is it possible to know the
electron’s momentum? Its velocity?
 Heisenberg Uncertainty Principle: Example
Consider an electron in the lowest-energy state of a hydrogen
atom; its position is known to an accuracy of about 0.05 nm (the
radius of the atom). How well is it possible to know the
electron’s momentum? Its velocity?

Solution:
xp   Heisenberg’s uncertainty principle (with  = h/2).

p  /x  = 1.0510-34 J·s.

= 2.110-24 J·s/m
= 2.110-24 kg-m/s

v= p/me me = 0.9110-30 kg.

= 2.3106 m/s
 Matter Waves...Quantitative

We will see that we can get good predictions (actually, so far they have never been wrong!!) by assuming that the state of a particle is described by a “wave function” (or “probability amplitude”):

(x,y,z,t)


What do we measure? Answer: (x,y,z,t)
--the probability density* for detecting a particle near some place (x,y,z), and at some time t.

We need a “wave equation” describing how (x,y,z,t) behaves. It should
 be as simple as possible
 make correct predictions

reduce to the usual classical laws of physics when applied to “classical” objects (e.g., baseballs)

*Probability per unit volume = ||2, i.e., ‘psi-squared’ (pronounced “sigh-squared”)

 The Schrödinger Equation
 In 1926, Erwin Schrödinger proposed an equation that
described the time- and space-dependence of the
wavefunction for matter waves (i.e., electrons, protons,...)
The Schrödinger Equation (SEQ)


There are two important forms for the SEQ
First we will focus on a very important special case of the SEQ, the
time-independent* SEQ, which is appropriate ONLY when the
particle’s wavefunction is associated with a single energy E (we’ll deal
with the more general case later). Also simplify (x,y,z)  (x).
(1-dimension)

 2 d 2  ( x) h
  U ( x ) ( x )  E  ( x ) 
2 m dx 2
2

*In this important case, which we’ll be primarily concerned with in

this course, the probability density || 2 associated with the
particle does not change with time…. it is in a “stationary state”.
 Time-Independent Schrödinger Eqn.
 What does the time-independent SEQ represent?

It’s actually not so puzzling…it’s just an expression of a familiar

result:
Kinetic Energy (KE) + Potential Energy (PE) = Total Energy (E)

 2 d 2 (x )
 2
 U ( x ) ( x )  E ( x )
2 m dx

KE term PE term Total E term

Consider :   cos(kx), p  k
The kinetic energy of the d 2 2
KE  2 d 2 (x )   k cos(kx )
particle is associated with dx 2

term: 2 m dx 2 the curvature of the 2 2 2 2 2
 d   k p
wavefunction, d2/dx2  2
  
2m dx 2m 2m
 Particle Wavefunctions: Examples
What do the solutions to the SEQ look like for general U(x)?
Examples of (x) for a particle in a given potential U(x): (different E)
(x) x x
We call these
wavefunctions
“states” of
the particle.

x x x

The corresponding probability distributions |(x)|2 of these states are:

  

x x x
Key point: Particle cannot be associated with a specific location x.
-- like the uncertainty that a particle went through slit 1 or slit 2.
 Exercise 2: Particle Wavefunction
The three wavefunctions below represent states of a particle
in the same potential U(x), and over the same range of x:
x x x
(a) (b) (c)

x x x

1. Which of these wavefunctions represents the particle with the

lowest kinetic energy? (Hint: Think “curvature”.)

2. Which corresponds to the highest kinetic energy?

 Exercise 2: Particle Wavefunction
The three wavefunctions below represent states of a particle
in the same potential U(x), and over the same range of x:
x x x
(a) (b) (c)
Highest Lowest
KE KE

x x x

1. Which of these wavefunctions represents the particle with the

lowest kinetic energy? (Hint: Think “curvature”.)
The curvature of the wavefunction  2 d 2  ( x) p2
 
represents kinetic energy: 2 m dx 2 2m

Since (b) clearly has the least curvature, that particle has lowest KE.
2. Which corresponds to the highest kinetic energy?
(a) has highest curvature  highest KE
 Supplementary Problem: Wavelengths
a) Calculate the wavelength of an electron that has been accelerated from rest across a
3-Volt potential difference (me = 9.1110-31 kg). [0.71 nm]

b) Do the same for a proton (mp = 1.6710-27 kg). [17 pm]

c) Calculate the wavelength of a major league fastball

(mbaseball = 0.15 kg, v = 50 m/s). [8.8 x 10-35 m]
 Supplementary Problem: Wavelengths
a) Calculate the wavelength of an electron that has been accelerated from rest across a
3-Volt potential difference (me = 9.1110-31 kg). [0.71 nm]

b) Do the same for a proton (mp = 1.6710-27 kg). [17 pm]

c) Calculate the wavelength of a major league fastball

(mbaseball = 0.15 kg, v = 50 m/s). [8.8 x 10-35 m]
Solution:
a)E = eV = 4.810-19 J This is from Physics 212.
p = (2meE) = 9.3510-25 kg m/s This is Physics 211.
 = h/p = 7.110-10 m = 0.71 nm This is Physics 214.

b) p = (2mpE) = 4.0010-23 kg m/s E is the same, because the electric charge is

 = h/p = 1.710-11 m the same. Mass is bigger   is smaller.

c) p = mv = 7.5 kg m/s SI units were designed to be convenient for

 = h/p = 8.810-35 m macroscopic objects.

Quantum mechanical wave effects are negligible in the motion of

macroscopic objects. The wavelength is many orders of magnitude