Chap.

2 Principles of Quantum Mechanics

• Motivation

- We need quantum mechanics to understand the basic properties of

solids such as energy bands

• Contents
- Birth of Quantum Mechanics
- Schrödinger Equation
- Applications of Schrödinger Equation
- Real-world Examples
 Birth of Quantum Mechanics

• Blackbody Radiation
• Photoelectric Effect
• Matter Wave
• Hydrogen Atom
• Uncertainty Principle
 Inconsistency of Classical Theory
• Blackbody radiation – particle nature of light

Pictures from wikipedia.org “Rayleigh-Jeans catastrophe”

Experimental behavior of blackbody radiation could be explained only after

Planck introduced an assumption that light consists of energy “quanta” called
photons, 𝐸𝐸 = 𝑛𝑛𝑛𝑛𝑛 (𝑛𝑛: integer, ℎ: Planck constant, 𝜈𝜈: frequency)
 Photoelectric effect

𝑇𝑇𝑚𝑚𝑚𝑚𝑚𝑚 = ℎ𝜈𝜈 − Φ
Work
function

Conceptual Physics by P. Hewitt

• Whether the plates emit electrons or not depends on the wavelength of the light
• Kinetic energy of emitted electrons depends linearly on the frequency of the light,
but not on the intensity of light
• Light behaves like particle having discrete energy with energy quantum 𝐸𝐸 = ℎ𝜈𝜈
 Emergence of Early Quantum Theory

• Matter wave – wave nature of a particle

Light seems to have a dual nature: particle-like nature of wave.
Why not for particles? Could matter (e.g. electrons), be wavelike?

• Lesson from the case of photon

In the theory of special relativity by Einstein,

𝐸𝐸 = 𝛾𝛾𝑚𝑚0 𝑐𝑐 2 = 𝑚𝑚02 𝑐𝑐 4 + 𝑝𝑝2 𝑐𝑐 2 where 𝛾𝛾 = 1⁄ 1 − 𝑣𝑣 2 ⁄𝑐𝑐 2

For a photon, which has zero rest mass (i.e. 𝑚𝑚0 = 0), 𝐸𝐸 = 𝑝𝑝𝑝𝑝
A photon has energy 𝐸𝐸 = ℎ𝜈𝜈
𝑐𝑐 ℎ De Broglie’s idea:
𝐸𝐸 = 𝑝𝑝𝑝𝑝 = ℎ𝜈𝜈 = ℎ ⇒ 𝑝𝑝 = Why don’t we generalize this to a
𝜆𝜆 𝜆𝜆
particle ?
 Experimental test for matter wave
Thompson’s experiment
(a) The experimental arrangement used by
Thomson to demonstrate a diffraction pattern
characteristic of the atomic arrangements in a
target of powdered aluminum. (b) The diffraction
pattern by (b) X-ray beam and (c) electron beam.
(a)

(b) (c)
Images from Fundamentals of Physics by Halliday, Resnick, & Walker

Experimental results by Thompson indicated that a particle beam having the

momentum corresponding to de Brogile wavelength comparable to X-ray
show the same diffraction pattern expected for that of X-ray with the same
wavelength when it is incident on a target specimen like powdered aluminum.
 Hydrogen atom
• Application of Quantum theory for shedding light on
atomic properties
http://chemistry.tutorvista.com/
Hot blackbody

Cloud of
cooler gas

Discrete spectral lines were observed in the emission/ absorption

spectra of H-gas (1906), making scientists puzzled and look for its
origin.
 Bohr’s Hydrogen Atom Model
Perspectives from de Broglie’s
matter wave

Niels Bohr made a bold

proposal to explain discrete
spectra of H atom:
- A stationary orbit is formed for an
electron if 𝐿𝐿 = 𝑚𝑚𝑚𝑚𝑚𝑚 = 𝑛𝑛𝑛.
- Light can be emitted or absorbed
when an electron changes its orbit
while satisfying
𝐸𝐸𝑖𝑖 − 𝐸𝐸𝑓𝑓 = ±ℎ𝜈𝜈
(+: emission, -: absorption)
from Conceptual Physics by P. Hewitt
Bohr’s condition for “stationary” orbit in
fact corresponds to the condition to
form “stationary (standing)” wave in a
circle (see the figure above)
𝑛𝑛𝜆𝜆𝑛𝑛 = 2𝜋𝜋𝑟𝑟𝑛𝑛 ,
𝜆𝜆𝑛𝑛 = 2𝜋𝜋⁄𝑘𝑘𝑛𝑛 = ℎ/𝑝𝑝𝑛𝑛 (𝑛𝑛 = 1,2,3, . . . )
∴ 𝐿𝐿𝑛𝑛 = 𝑟𝑟𝑛𝑛 𝑝𝑝𝑛𝑛 = 𝑛𝑛𝑛/2𝜋𝜋 = 𝑛𝑛𝑛
 Bohr’s Hydrogen Atom Model
Bohr’s theory was quite successful in that it was able to predict the
discrete energy levels associated with each stationary orbit and
thus discrete emission/absorption spectra in a quantitative way.

=
1 e2 mv2
4πε 0 r 2 r
(
(1) ← Coulomb force= cent rifugal force )
(mvr )v (n )v e2
= = →=
v = vn (2)
r 2
r 2
4πε 0
n 

Combining (1) and (2),

( )
2
1 e 2
1 e 4πε 0n 2
n 2 4πε 02 n 2ε 02
=rn = = = = n 2aB (3)
4πε 0 mvn 2
4πε 0 m e 4
me 2
me π 2

where aB = 0.53A= Bohr radius.

Combining (1) and (3),

1 1 e2 1 e2 1 e2
E n = T + V = mvn −
2
= −
2 4πε 0 rn 8πε 0 rn 4πε 0 rn
1 e2 1  me4  13.6eV
=
− =
− 2 =− (4)
8πε 0 rn n  8ε 0h 2  n2
 Uncertainty Principle
• Classical wave packets:
- Spatial spread of a wave packet: Δ𝑥𝑥
- Momentum spread of a wave packet: Δ𝑘𝑘
Δ𝑥𝑥Δ𝑘𝑘~2𝜋𝜋
• Electrons have similar properties:
(Uncertainty Principle)
𝛥𝛥𝛥𝛥𝛥𝛥𝛥𝛥 = Δ𝑥𝑥 ℏΔ𝑘𝑘 ≥ ℎ
Δ𝐸𝐸Δ𝑡𝑡 ≥ ℎ

- The most fundamental principle of quantum mechanics, associated

with the concept of wave function and its probabilistic interpretation

- Everything in quantum mechanics breaks down if this uncertainty

principle is found to be invalid!
 Uncertainty
Principle
Δ𝑥𝑥𝑥𝑥𝑥 ≥ ℎ
This means that, if one wants to measure the position of a particle (electron)
and its momentum simultaneously, one cannot measure both accurately. That
is, if one wants to measure the position more accurately, he/she has to lose
the accuracy of the momentum.

Δ𝐸𝐸Δ𝑡𝑡 ≥ ℎ
This also has to with measurement. What the above uncertainty principle implies
is that, if one wants to measure an energy level of a particle more accurately
(smaller ΔE), the particle has to be stay at the level for longer time (larger Δt). For
example, suppose that a particle is confined in a box and we measure its energy
when the particle comes out of the box. If we want to measure its energy more
accurately, we have to wait longer.
 Schrödinger Equation

• Schrödinger Equation
• Meaning of the Wave Function
 Intuitive Derivation of
the Time-independent Schrödinger Equation

• From basic electromagnetics, simple Helmholtz equation is

given by 2 2 2 𝜕𝜕2 𝜕𝜕2 𝜕𝜕2
𝛻𝛻 𝜓𝜓 + 𝑘𝑘 𝜓𝜓 = 0 (𝛻𝛻 ≡ 2 + 2 + 2 )
𝜕𝜕𝑥𝑥 𝜕𝜕𝑦𝑦 𝜕𝜕𝑧𝑧
– Review electromagnetics, if you cannot understand the above equation

– The wavevector magnitude k is given by

– From de Broglie wavelength, where

• Therefore, we can rewrite the wave equation as follows

−ℏ2 𝛻𝛻 2 𝜓𝜓 = 𝑝𝑝2 𝜓𝜓
ℏ2 2 𝑝𝑝2
− 𝛻𝛻 𝜓𝜓 = 𝜓𝜓
2𝑚𝑚 2𝑚𝑚
mass of free electron
 Intuitive Derivation of
the Time-independent Schrödinger Equation

• Note that (p2/2m) is electron’s kinetic energy, and in general,

(Total energy)=(Kinetic energy) + (Potential energy)
• Therefore,
ℏ2 2 𝑝𝑝2 ℏ2 2
− 𝛻𝛻 𝜓𝜓 = 𝜓𝜓 − 𝛻𝛻 𝜓𝜓 = 𝐸𝐸 − 𝑉𝑉 𝜓𝜓
2𝑚𝑚 2𝑚𝑚 2𝑚𝑚
Total Potential
Energy Energy
ℏ2 2
• Or, equivalently, − 𝛻𝛻 𝜓𝜓 + 𝑉𝑉𝑉𝑉 = 𝐸𝐸𝐸𝐸
2𝑚𝑚

• Note that this is not the derivation of Schrödinger equation

– There is no way to derive Schrödinger equation from the first principle
– It has to be postulated, like Newton’s laws are postulated
Another Intuitive Derivation of the Schrödinger equation
• Energy = kinetic energy + potential energy
𝑝𝑝2
𝐸𝐸 = 𝑇𝑇 + 𝑉𝑉 = + 𝑉𝑉(𝑥𝑥)
2𝑚𝑚
• In quantum mechanics, physical observables like position, momentum,
and energy becomes ‘operators’:
ℏ 𝜕𝜕 𝜕𝜕
𝑥𝑥 → 𝑥𝑥, 𝑝𝑝 → , 𝐸𝐸 → 𝑖𝑖𝑖
𝑖𝑖 𝜕𝜕𝜕𝜕 𝜕𝜕𝜕𝜕

• Using the operators,

1 2
𝐸𝐸 = 𝑝𝑝 + 𝑉𝑉(𝑥𝑥)
2𝑚𝑚
2
𝜕𝜕 1 ℏ 𝜕𝜕
𝑖𝑖𝑖 = + 𝑉𝑉(𝑥𝑥)
𝜕𝜕𝜕𝜕 2𝑚𝑚 𝑖𝑖 𝜕𝜕𝜕𝜕

• introducing “wave function” 𝜓𝜓(𝑥𝑥, 𝑡𝑡)

𝜕𝜕 ℏ2 𝜕𝜕 2
𝑖𝑖𝑖 𝜓𝜓(𝑥𝑥, 𝑡𝑡) = − + 𝑉𝑉 𝑥𝑥 𝜓𝜓(𝑥𝑥, 𝑡𝑡) : the time-dependent
𝜕𝜕𝜕𝜕 2𝑚𝑚 𝜕𝜕𝑥𝑥 2 Schrödinger equation
Comparison between the Schrödinger wave
equation and classical wave equation

Schrödinger Wave Equation

ℏ2 𝜕𝜕 2 𝜕𝜕
− 2
+ 𝑉𝑉 𝑥𝑥 𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝑖𝑖𝑖 𝜓𝜓(𝑥𝑥, 𝑡𝑡)
2𝑚𝑚 𝜕𝜕𝑥𝑥 𝜕𝜕𝜕𝜕

Classical Wave Equation

𝜕𝜕 2 1 𝜕𝜕 2
𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 2 2 𝜓𝜓(𝑥𝑥, 𝑡𝑡)
𝜕𝜕𝑥𝑥 2 𝑣𝑣 𝜕𝜕𝑡𝑡
 Time-independent Schrödinger equation

• If the potential 𝑉𝑉 is time-independent, i.e. 𝑉𝑉 𝑥𝑥, 𝑡𝑡 = 𝑉𝑉(𝑥𝑥)

• We try 𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝜓𝜓 𝑥𝑥 𝜙𝜙(𝑡𝑡) (‘separation of variables’ technique)

ℏ2 𝜕𝜕 2 𝜕𝜕
𝜙𝜙 𝑡𝑡 − + 𝑉𝑉 𝜓𝜓 𝑥𝑥 = 𝑖𝑖𝑖𝑖𝑖 𝑥𝑥 𝜙𝜙 𝑡𝑡
2𝑚𝑚 𝜕𝜕𝑥𝑥 2 𝜕𝜕𝜕𝜕
1 ℏ2 𝜕𝜕 2 1 𝜕𝜕
− + 𝑉𝑉 𝜓𝜓 𝑥𝑥 = 𝑖𝑖𝑖 𝜙𝜙 𝑡𝑡 = 𝐸𝐸 (a constant)
𝜓𝜓 𝑥𝑥 2𝑚𝑚 𝜕𝜕𝑥𝑥 2 𝜙𝜙 𝑡𝑡 𝜕𝜕𝜕𝜕
𝑖𝑖𝑖𝑖
𝜕𝜕𝜕𝜕 − ℏ 𝑡𝑡
• Temporal part: 𝑖𝑖𝑖 = 𝐸𝐸𝐸𝐸 → 𝜙𝜙 𝑡𝑡 = 𝑒𝑒
𝜕𝜕𝜕𝜕
• Spatial part:
ℏ2 𝝏𝝏𝟐𝟐
− + 𝑉𝑉 𝜓𝜓 𝑥𝑥 = 𝐸𝐸𝐸𝐸 𝑥𝑥 ( time-independent Schrödinger Eq.)
2𝑚𝑚 𝝏𝝏𝒙𝒙 𝟐𝟐

• Full solution with both the spatial and time parts:

𝑖𝑖𝑖𝑖
𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝜓𝜓 𝑥𝑥 𝜙𝜙 𝑡𝑡 = 𝜓𝜓 𝑥𝑥 𝑒𝑒 − ℏ 𝑡𝑡
 Meaning of the Wave Function

• Hint from light (electromagnetic wave / photon)

2
1 𝑑𝑑 𝐸𝐸(𝑥𝑥, 𝑡𝑡)
𝛻𝛻 2 𝐸𝐸(𝑥𝑥, 𝑡𝑡) − 2 =0
𝑐𝑐 𝑑𝑑𝑡𝑡 2

𝜆𝜆1 = 2𝐿𝐿, 𝜆𝜆2 = 𝐿𝐿, …

M 𝐼𝐼 ∝ 𝐸𝐸(𝑥𝑥) 2 M
∝ 𝑁𝑁𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝 (𝑥𝑥)

Number density (per length) of photons ~ proportional to the

squared magnitude of the associated wave amplitude
 Meaning of the Wave Function
• Hint from light (electromagnetic wave / photon)

~30 photons ~1000 photons ~10000 photons

Hewitt, Conceptual Physics

 Probability Density, |ψ|2

• The probability density P(r) of finding the electron at any

specific point r in space is proportional to |ψ(r)|2
– note that the probability of finding a photon at any point in space is
proportional to the square of the electric field wave (intensity or electric
energy density are proportional to the square of the electric field)
– In classical mechanics, the position of a particle can be determined
precisely, whereas in quantum mechanics, the position of a particle is
found in terms of a probability

• Or, equivalently,

• From the definition of probability,

∞
2 𝑑𝑑𝑑𝑑
• For one-dimensional case, � 𝜓𝜓 𝑥𝑥 =1
−∞
 Wavefunction, ψ

• In addition to ∫ 𝝍𝝍 𝒓𝒓 𝟐𝟐 𝒅𝒅𝟑𝟑 𝒓𝒓 = 𝟏𝟏, 𝝍𝝍(𝒓𝒓) has to meet the

following boundary conditions.

– Condition 1. It must be finite, single-valued, and continuous.

– Condition 2. Its derivative, 𝛻𝛻𝜓𝜓(𝑟𝑟), must be finite, single-valued, and
continuous.

– In special cases where the potential function, V, becomes infinite in

particular regions of space, the first derivative will not necessarily be
continuous, but the remaining boundary conditions will still hold.
Applications of Schrödinger Equation

• Electron in free space

• Infinite barrier Problem
• Step barrier
• Tunneling
 Electron in Free space
• In free space, potential 𝑉𝑉 𝑥𝑥 = 0

ℏ2 𝝏𝝏𝟐𝟐
− 𝜓𝜓 𝑥𝑥 = 𝐸𝐸𝐸𝐸 𝑥𝑥 ---- (1)
2𝑚𝑚 𝝏𝝏𝒙𝒙𝟐𝟐

𝝏𝝏𝟐𝟐
𝝏𝝏𝒙𝒙𝟐𝟐
𝜓𝜓 𝑥𝑥 + 2𝑚𝑚𝑚𝑚
ℏ2
𝜓𝜓 𝑥𝑥 = 0 ---- (2)

≡ 𝒌𝒌𝟐𝟐

• The solution is :

𝜓𝜓 𝑥𝑥 = 𝐴𝐴𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖 + 𝐵𝐵𝑒𝑒 −𝑖𝑖𝑖𝑖𝑖𝑖 --- (3)

• The total wave function :

𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝜓𝜓 𝑥𝑥 𝑒𝑒 −𝑖𝑖𝑖𝑖𝑖𝑖 = 𝐴𝐴𝑒𝑒 𝑖𝑖(𝑘𝑘𝑘𝑘−𝜔𝜔𝜔𝜔) + 𝐵𝐵𝑒𝑒 −𝑖𝑖(𝑘𝑘𝑘𝑘+𝜔𝜔𝜔𝜔) --- (4)

 Electron in Free space
• Let’s consider an electron traveling in the +𝑥𝑥 direction:

𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝐴𝐴𝑒𝑒 𝑖𝑖(𝑘𝑘𝑘𝑘−𝜔𝜔𝜔𝜔)

2𝑚𝑚𝑚𝑚 𝑝𝑝2 𝑝𝑝
𝑘𝑘 = = =
ℏ2 ℏ2 ℏ

• We can see that the de Broglie’s relationship 𝑝𝑝 = ℏ𝑘𝑘 is recovered

(or this justifies our interpretation of 𝑘𝑘 as the wave number)

• Electron expressed by the above wave function (or plane wave)

- has a definite energy 𝐸𝐸 and definite momentum 𝑝𝑝
- in other words, Δ𝑝𝑝 = 0
- this implies that from the uncertainty principle, Δ𝑥𝑥 = ∞
- that is, “the electron” is spread all over the space
- this is consistent with the fact that
2 𝑖𝑖𝑖𝑖𝑖𝑖−𝜔𝜔𝜔𝜔 2
𝜓𝜓 𝑥𝑥, 𝑡𝑡 = 𝐴𝐴𝑒𝑒 = 𝐴𝐴2 = 𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
so, electron can be found anywhere with equal probability
 Energy vs. Momentum for Free Particle
𝑝𝑝2 ℏ2 𝑘𝑘 2
𝐸𝐸 = =
2𝑚𝑚 2𝑚𝑚

𝑝𝑝 = 2𝑚𝑚𝑚𝑚

2𝑚𝑚𝑚𝑚
𝑘𝑘 =
ℏ

2𝜋𝜋 ℎ
𝜆𝜆 = =
𝑘𝑘 2𝑚𝑚𝑚𝑚
k

A free particle with a well-defined energy will also have a well-defined

wavelength and momentum.
 Applications of Schrödinger Equation

Quantum confinement e
(electrons are confined in space
Two cases within a potential)

Transmission problem e
(electrons are incident from the left
and transmit through a potential
barrier(s) to the right)

• Confinement: bound state  discrete energy levels (eigenvalue problem)

• Transmission problem: unbound state  transmission/tunneling probability

In both the cases, our objective is to find the wave function 𝜓𝜓

The infinite potential well

• Potential

0 if 0 < 𝑥𝑥 < 𝑎𝑎
𝑉𝑉 𝑥𝑥 = �
∞ otherwise

• Solution of Schrödinger equation inside the

well (Region II)

ℏ2 𝜕𝜕 2
− 𝜓𝜓 𝑥𝑥 = 𝐸𝐸𝐸𝐸 𝑥𝑥
2𝑚𝑚 𝜕𝜕𝑥𝑥 2
2𝑚𝑚𝑚𝑚
where 𝑘𝑘 =
ℏ2
 The infinite potential well
• At the boundaries :

𝜓𝜓 𝑥𝑥 = 0 = 𝐴𝐴 + 𝐵𝐵 = 0 1 1 𝐴𝐴 0
= --- (1)
𝑒𝑒 −𝑖𝑖𝑖𝑖𝑖𝑖 𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖 𝐵𝐵 0
𝜓𝜓 𝑥𝑥 = 𝑎𝑎 = 𝐴𝐴𝑒𝑒 −𝑖𝑖𝑖𝑖𝑖𝑖 + 𝐵𝐵𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖 = 0

• Non-trivial solution of 𝐴𝐴 ≠ 0 and 𝐵𝐵 ≠ 0 exists if

1 1
−𝑖𝑖𝑖𝑖𝑖𝑖 = 𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖 − 𝑒𝑒 −𝑖𝑖𝑖𝑖𝑖𝑖 = 2 sin( 𝑘𝑘𝑘𝑘) = 0 --- (2)
𝑒𝑒 𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖

∴ 𝑘𝑘𝑘𝑘 = 𝑛𝑛𝑛𝑛 where 𝑛𝑛 = 1,2, …

𝑛𝑛𝑛𝑛 2𝜋𝜋 2𝑎𝑎 𝜆𝜆

𝑘𝑘𝑛𝑛 = → 𝜆𝜆n = = i. e. 𝑎𝑎 = 𝑛𝑛 --- (3)
𝑎𝑎 𝑘𝑘𝑛𝑛 𝑛𝑛 2
 The infinite potential well
ℏ2 𝑘𝑘𝑛𝑛2 ℏ2 𝑛𝑛2 𝜋𝜋 2
• Energy 𝐸𝐸𝑛𝑛 = =
2𝑚𝑚 2𝑚𝑚 𝑎𝑎2

• Energy levels and eigenfunctions

𝐸𝐸4 = 16𝐸𝐸1 = ℏ𝜔𝜔4 2 4𝜋𝜋
𝜓𝜓4 𝑥𝑥 = sin 𝑥𝑥
𝑎𝑎 𝑎𝑎
𝐸𝐸3 = 9𝐸𝐸1 = ℏ𝜔𝜔3 2 3𝜋𝜋
𝜓𝜓3 𝑥𝑥 = sin 𝑥𝑥
𝑎𝑎 𝑎𝑎

𝐸𝐸2 = 4𝐸𝐸1 = ℏ𝜔𝜔2 2 2𝜋𝜋

𝜓𝜓2 𝑥𝑥 = sin 𝑥𝑥
𝑎𝑎 𝑎𝑎
ℏ2 𝜋𝜋 2
𝐸𝐸1 = = ℏ𝜔𝜔1 2 𝜋𝜋
2𝑚𝑚𝑎𝑎2 𝜓𝜓1 𝑥𝑥 = sin 𝑥𝑥
𝑎𝑎 𝑎𝑎 Four lowest Corresponding Corresponding
discrete energy wave functions probability
• Time-dependent wave-function: levels functions

𝜓𝜓𝑛𝑛 𝑥𝑥, 𝑡𝑡 = 𝜓𝜓𝑛𝑛 𝑥𝑥 𝑒𝑒 −𝑖𝑖𝜔𝜔𝑛𝑛 𝑡𝑡

2 ℏ𝑘𝑘𝑛𝑛2
= sin 𝑘𝑘𝑛𝑛 𝑥𝑥 𝑒𝑒 −𝑖𝑖𝜔𝜔𝑛𝑛 𝑡𝑡 , where 𝜔𝜔𝑛𝑛 =
𝑎𝑎 2𝑚𝑚
 Energy vs. Momentum for
Particle in the Infinite Potential Well
• The possible values for energy and momentum are now
‘quantized’

ℏ2 𝑛𝑛𝑛𝑛 2
𝐸𝐸𝑛𝑛 =
2𝑚𝑚 𝑎𝑎

𝜋𝜋𝜋
𝑝𝑝𝑛𝑛 = 𝑛𝑛
𝑎𝑎
 The finite potential well

𝑈𝑈0 • Potential
0 if 0 < 𝑥𝑥 < 𝑎𝑎
𝑉𝑉 𝑥𝑥 = �
𝑈𝑈0 otherwise
0 0

• Solution: there are “quantized energy levels” inside the well

(quantized energy levels)

(wave functions)
 Other confinement potentials

“triangular-like potential” “parabolic potential”

Even (node = 1)  Odd (node = 2)  Even (node = 3)  ….

Transmission Problem: The Step Potential Function

• Schrödinger equation
Region
Region 1 2 ℏ2 𝜕𝜕 2
In Region 1 : − 𝜓𝜓 = 𝐸𝐸𝜓𝜓1
2𝑚𝑚 𝜕𝜕𝑥𝑥 2 1
ℏ2 𝜕𝜕 2
In Region 2 : − 𝜓𝜓 + 𝑉𝑉𝑜𝑜 𝜓𝜓2 = 𝐸𝐸𝜓𝜓2
2𝑚𝑚 𝜕𝜕𝑥𝑥 2 2

• Solution (the case of 𝐸𝐸 > 𝑉𝑉0 )

2𝑚𝑚𝑚𝑚
Region 1 : 𝜓𝜓1 = 𝐴𝐴𝑒𝑒 𝑖𝑖𝑘𝑘1𝑥𝑥 + 𝐵𝐵𝑒𝑒 −𝑖𝑖𝑘𝑘1𝑥𝑥 , 𝑘𝑘1 =
ℏ
2𝑚𝑚 𝐸𝐸 − 𝑉𝑉𝑜𝑜
Region 2 : 𝜓𝜓2 = 𝐶𝐶𝑒𝑒 𝑖𝑖𝑘𝑘2𝑥𝑥 , 𝑘𝑘2 =
ℏ
 Transmission Problem: The Step Potential Function

• The boundary conditions “crude” justification

From current continuity
𝜓𝜓𝐼𝐼 𝑥𝑥 = 0 = 𝜓𝜓𝐼𝐼𝐼𝐼 𝑥𝑥 = 0 ℏ𝑘𝑘1 𝑒𝑒𝑒
𝑗𝑗1 = 𝑒𝑒𝜐𝜐1 ∝ 𝑒𝑒 = 𝑖𝑖𝑖
𝜕𝜕
𝐵𝐵 𝐶𝐶 𝑚𝑚 𝑚𝑚 𝜕𝜕𝜕𝜕
𝐴𝐴 + 𝐵𝐵 = 𝐶𝐶 → 1 + = (1) ℏ𝑘𝑘2 𝑒𝑒𝑒 𝜕𝜕
𝐴𝐴 𝐴𝐴 = 𝑒𝑒𝜐𝜐2 ∝ 𝑒𝑒
𝑚𝑚
=
𝑚𝑚
𝑖𝑖𝑖
𝜕𝜕𝜕𝜕
𝜕𝜕𝜓𝜓1 𝜕𝜕𝜓𝜓2
𝜕𝜕 𝜕𝜕 ∴
𝜕𝜕𝜕𝜕
=
𝜕𝜕𝜕𝜕
𝜓𝜓 � = 𝜓𝜓 �
𝜕𝜕𝜕𝜕 𝐼𝐼 𝑥𝑥=0 𝜕𝜕𝜕𝜕 𝐼𝐼𝐼𝐼 𝑥𝑥=0
If the masses of the two regions
𝐵𝐵 𝑘𝑘2 𝐶𝐶 are different, the current
1− = ⋅ (2) continuity leads to
𝐴𝐴 𝑘𝑘1 𝐴𝐴
1 𝜕𝜕𝜓𝜓1 1 𝜕𝜕𝜓𝜓2
=
𝑚𝑚1 𝜕𝜕𝜕𝜕 𝑚𝑚2 𝜕𝜕𝜕𝜕

• Note that this is NOT an eigenvalue problem; i.e. the incident electron has
the continuous energy levels (0 < 𝐸𝐸 < ∞)
Transmission Problem: The Step Potential Function
• Solution from (1) & (2) :
𝑘𝑘2 𝐶𝐶 𝐶𝐶 2
2= 1+ ⋅ → =
𝑘𝑘1 𝐴𝐴 𝐴𝐴 1 + 𝑘𝑘2 ⁄𝑘𝑘1
𝐵𝐵 𝐶𝐶 𝑘𝑘2 𝑘𝑘2
= −1= 1− � 1+
𝐴𝐴 𝐴𝐴 𝑘𝑘1 𝑘𝑘1
𝑒𝑒𝑒
𝐽𝐽𝐼𝐼 = 𝑘𝑘1 ⋅ 𝐴𝐴 2 (incident flux)
𝑚𝑚
𝑒𝑒𝑒
• Current Flux 𝐽𝐽𝑅𝑅 = 𝑘𝑘1 ⋅ 𝐵𝐵 2 (reflected flux)
𝑚𝑚
𝑒𝑒𝑒
𝐽𝐽𝑇𝑇 = 𝑘𝑘2 ⋅ 𝐶𝐶 2 (transmitted flux)
𝑚𝑚
2 2
𝐽𝐽 𝐵𝐵 1 − 𝑘𝑘2 ⁄𝑘𝑘1
• Reflection coefficient 𝑅𝑅 = 𝑅𝑅 = 2 = 2
𝐽𝐽𝐼𝐼 𝐴𝐴 1 + 𝑘𝑘2 ⁄𝑘𝑘1

𝐽𝐽𝑇𝑇 𝑘𝑘2 𝐶𝐶 2 4𝑘𝑘2 1

• Transmission coefficient 𝑇𝑇 = = = ⋅
𝐽𝐽𝐼𝐼 𝑘𝑘1 𝐴𝐴 2 𝑘𝑘1 1 + 𝑘𝑘2 ⁄𝑘𝑘1 2

= 1 − 𝑅𝑅
⇒ 𝑇𝑇 + 𝑅𝑅 = 1
Transmission Problem: The Step Potential Function
• What happens if 𝐸𝐸 < 𝑉𝑉0 ?

• Schrödinger equation
𝐸𝐸
𝑉𝑉𝑜𝑜 ℏ2 𝜕𝜕
In Region 1 : − 𝜓𝜓 = 𝐸𝐸𝜓𝜓1
2𝑚𝑚 𝜕𝜕𝑥𝑥 2 1
Region 1 Region 2
ℏ2 𝜕𝜕
In Region 2: − 𝜓𝜓 + 𝑉𝑉0 𝜓𝜓2 = 𝐸𝐸𝜓𝜓2
𝑥𝑥 = 0 2𝑚𝑚 𝜕𝜕𝑥𝑥 2 2

• Similar to the previous case, but

2𝑚𝑚𝑚𝑚
𝜓𝜓1 = 𝐴𝐴𝑒𝑒 𝑖𝑖𝑘𝑘1 𝑥𝑥 + 𝐵𝐵𝑒𝑒 −𝑖𝑖𝑘𝑘1 𝑥𝑥 𝑘𝑘1 =
ℏ

2𝑚𝑚(𝑉𝑉0 −𝐸𝐸)
𝜓𝜓2 = 𝐶𝐶𝑒𝑒 −𝜅𝜅2𝑥𝑥 𝜅𝜅2 =
ℏ

• R = 1, and T = 0
 The Step Potential Function
( in terms of “wave” picture)

Case : 𝐸𝐸 > 𝑉𝑉0

2
𝐽𝐽𝑅𝑅 𝐵𝐵
𝐵𝐵𝑒𝑒 𝑖𝑖 −𝑘𝑘1 𝑥𝑥−𝜔𝜔𝜔𝜔
𝑅𝑅 = =
𝐽𝐽𝐼𝐼 𝐴𝐴
𝐶𝐶𝑒𝑒 𝑖𝑖 𝑘𝑘2 𝑥𝑥−𝜔𝜔𝜔𝜔

𝐸𝐸
2
𝐽𝐽𝑇𝑇 𝑘𝑘2 𝐶𝐶
𝐴𝐴𝑒𝑒 𝑖𝑖 𝑘𝑘1 𝑥𝑥−𝜔𝜔𝜔𝜔 𝑇𝑇 = =
𝐽𝐽𝐼𝐼 𝑘𝑘1 𝐴𝐴
𝑉𝑉𝑜𝑜
 What do T and R mean ?
(in terms of “particle” picture)
Case : 𝐸𝐸 > 𝑉𝑉0
For example: 𝑅𝑅 = 0.3, 𝑇𝑇 = 0.7

300
700
𝐸𝐸

1000
𝑉𝑉𝑜𝑜

• Suppose we are doing a scattering experiment with “electron particle”

- Total number of trial = 1000 times
- Transmitted = 700 times (expected value)
- Reflected = 300 times (expected value)
 Transmission as a Function of Energy

Case : 𝐸𝐸 > 𝑉𝑉0

𝐵𝐵𝑒𝑒 𝑖𝑖 −𝑘𝑘1 𝑥𝑥−𝜔𝜔𝜔𝜔

𝐶𝐶𝑒𝑒 𝑖𝑖 𝑘𝑘2 𝑥𝑥−𝜔𝜔𝜔𝜔

𝐸𝐸

𝐴𝐴𝑒𝑒 𝑖𝑖 𝑘𝑘1 𝑥𝑥−𝜔𝜔𝜔𝜔

𝑉𝑉𝑜𝑜

0 1
𝑇𝑇(𝐸𝐸)

• If 𝐸𝐸 ≫ 𝑉𝑉0 , almost no reflection (like classical particle)

• If 𝐸𝐸 becomes closer to 𝑉𝑉0 , reflection increases sharply
 The Step Potential function

Case : 𝐸𝐸 < 𝑉𝑉0

𝐵𝐵𝑒𝑒 𝑖𝑖 −𝑘𝑘1 𝑥𝑥−𝜔𝜔𝜔𝜔 𝐽𝐽𝑅𝑅 𝐵𝐵 2

𝑅𝑅 = = = 1
𝐽𝐽𝐼𝐼 𝐴𝐴
𝐸𝐸

𝑇𝑇 = 1 − 𝑅𝑅 = 0
𝐶𝐶𝑒𝑒 −𝑘𝑘2 𝑥𝑥
𝐴𝐴𝑒𝑒 𝑖𝑖 𝑘𝑘1 𝑥𝑥−𝜔𝜔𝜔𝜔 𝑉𝑉𝑜𝑜

|𝜓𝜓|2 = |𝐶𝐶|2 𝑒𝑒 −2𝑘𝑘2 𝑥𝑥

There’s non-zero probability to find electrons here! But R = 1.
 In terms of “particle” picture
Case : 𝐸𝐸 < 𝑉𝑉0
𝐽𝐽𝑅𝑅 𝐵𝐵 2
𝑅𝑅 = = = 1
𝐽𝐽𝐼𝐼 𝐴𝐴

1000 𝑇𝑇 = 1 − 𝑅𝑅 = 0
𝐸𝐸
𝐶𝐶𝑒𝑒 −𝑘𝑘2 𝑥𝑥
900 𝑉𝑉𝑜𝑜
100

• Suppose we are doing a scattering experiment with “electron particle”

• An example:
- Total number of trial = 1000 times
- Directly Bounce back (without penetration) = 900 times
- Penetrate into inside of the step, then bounce back eventually = 100 times
 Step Potential Simulation

• http://phet.colorado.edu/en/simulation/quantum-tunneling
 Potential barrier and tunneling

Under the barrier ( 𝑬𝑬 < 𝑽𝑽𝟎𝟎 ) • Wave functions in each region

2𝑚𝑚𝑚𝑚
𝜓𝜓1 𝑥𝑥 = 𝐴𝐴𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖 + 𝐵𝐵𝑒𝑒 −𝑖𝑖𝑖𝑖𝑖𝑖 𝑘𝑘 =
ℏ
2𝑚𝑚 𝑉𝑉0 −𝐸𝐸
𝐴𝐴
𝐹𝐹 𝜓𝜓2 𝑥𝑥 = 𝐶𝐶𝑒𝑒 𝜅𝜅𝑥𝑥 + 𝐷𝐷𝑒𝑒 −𝜅𝜅𝑥𝑥 𝜅𝜅 =
𝐶𝐶 ℏ
E
𝐵𝐵 𝑉𝑉𝑜𝑜 𝜓𝜓3 𝑥𝑥 = 𝐹𝐹𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖
𝐷𝐷

1 2 3 • Boundary conditions
𝑥𝑥 = 0 𝑥𝑥 = 𝑎𝑎
𝑥𝑥 = 0 𝑥𝑥 = 𝑎𝑎
𝐴𝐴 + 𝐵𝐵 = 𝐶𝐶 + 𝐷𝐷 𝐶𝐶𝑒𝑒 𝜅𝜅𝜅𝜅 + 𝐷𝐷𝑒𝑒 −𝜅𝜅𝜅𝜅 = 𝐹𝐹𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖
𝑖𝑖𝑖𝑖 𝐴𝐴 − 𝐵𝐵 = 𝜅𝜅(𝐶𝐶 − 𝐷𝐷) 𝜅𝜅 𝐶𝐶𝑒𝑒 𝜅𝜅𝜅𝜅 − 𝐷𝐷𝑒𝑒 −𝜅𝜅𝜅𝜅 = 𝑖𝑖𝑖𝑖𝑖𝑖𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖

Transmission
𝐹𝐹 4𝑖𝑖𝑖𝑖/𝜅𝜅
= 2 𝜅𝜅𝜅𝜅 2 −𝜅𝜅𝜅𝜅
𝑒𝑒 −𝑖𝑖𝑖𝑖𝑖𝑖
𝐴𝐴 − 1 − 𝑖𝑖𝑖𝑖/𝜅𝜅 𝑒𝑒 + 1 + 𝑖𝑖𝑖𝑖/𝜅𝜅 𝑒𝑒
2
𝐹𝐹 1
𝑇𝑇 = =
𝐴𝐴 𝑘𝑘 2 + 𝜅𝜅 2
1+ sinh2 𝜅𝜅𝜅𝜅
2𝑘𝑘𝑘𝑘
 Particle Tunneling (under the barrier)
From nanoHUB
(ABACUS, piecewise-constant-potential lab)

T(E)

1 nm

• Transmission
2
𝐹𝐹 1
𝑇𝑇 = = 2
𝐴𝐴 𝑘𝑘 2 + 𝜅𝜅 2 2 nm
1+ sinh2 𝜅𝜅𝜅𝜅
2𝑘𝑘𝑘𝑘

• When 𝑎𝑎 becomes large, 𝑇𝑇 𝐸𝐸 ~𝑒𝑒 −2𝜅𝜅𝜅𝜅

• When 𝐸𝐸 ≪ 𝑉𝑉0 ,
𝐸𝐸 𝐸𝐸
𝑇𝑇 𝐸𝐸 ~16 1− 𝑒𝑒 −2𝜅𝜅𝜅𝜅 3 nm
𝑉𝑉0 𝑉𝑉0
0 1
 Potential barrier and tunneling

Over the barrier ( 𝑬𝑬 > 𝑽𝑽𝟎𝟎 ) • Wave functions in each region

2𝑚𝑚𝑚𝑚
𝜓𝜓1 𝑥𝑥 = 𝐴𝐴𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖 + 𝐵𝐵𝑒𝑒 −𝑖𝑖𝑖𝑖𝑖𝑖 𝑘𝑘 =
E ℏ
′ 𝑥𝑥 ′ 𝑥𝑥 2𝑚𝑚 𝐸𝐸−𝑉𝑉0
𝐴𝐴
𝐹𝐹 𝜓𝜓2 𝑥𝑥 = 𝐶𝐶𝑒𝑒 𝑖𝑖𝑘𝑘 + 𝐷𝐷𝑒𝑒 −𝑖𝑖𝑘𝑘 𝑘𝑘 ′ =
𝐶𝐶 ℏ
𝑉𝑉𝑜𝑜
𝐵𝐵
𝐷𝐷 𝜓𝜓3 𝑥𝑥 = 𝐹𝐹𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖

1 2 3 • Boundary conditions
𝑥𝑥 = 0 𝑥𝑥 = 𝑎𝑎
𝑥𝑥 = 0 𝑥𝑥 = 𝑎𝑎
′ ′
𝐴𝐴 + 𝐵𝐵 = 𝐶𝐶 + 𝐷𝐷 𝐶𝐶𝑒𝑒 𝑖𝑖𝑘𝑘 𝑎𝑎 + 𝐷𝐷𝑒𝑒 −𝑖𝑖𝑘𝑘 𝑎𝑎 = 𝐹𝐹𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖
′ ′
𝑖𝑖𝑖𝑖 𝐴𝐴 − 𝐵𝐵 = 𝑖𝑖𝑖𝑖𝑖(𝐶𝐶 − 𝐷𝐷) 𝑖𝑖𝑖𝑖𝑖 𝐶𝐶𝑒𝑒 𝑖𝑖𝑘𝑘 𝑎𝑎 − 𝐷𝐷𝑒𝑒 −𝑖𝑖𝑘𝑘 𝑎𝑎 = 𝑖𝑖𝑖𝑖𝑖𝑖𝑒𝑒 𝑖𝑖𝑖𝑖𝑖𝑖

Transmission
𝐹𝐹 4𝑘𝑘/𝑘𝑘𝑘
= 2 𝜅𝜅𝜅𝜅 2 −𝜅𝜅𝜅𝜅
𝑒𝑒 −𝑖𝑖𝑖𝑖𝑖𝑖
𝐴𝐴 − 1 − 𝑘𝑘/𝑘𝑘𝑘 𝑒𝑒 + 1 + 𝑘𝑘/𝑘𝑘𝑘 𝑒𝑒
2
𝐹𝐹 1
𝑇𝑇 = =
𝐴𝐴 𝑘𝑘 2 − 𝑘𝑘 ′ 2
1+ sin2 𝑘𝑘𝑘𝑎𝑎
2𝑘𝑘𝑘𝑘′
 Particle Transmission (Over the barrier)

E
𝑉𝑉𝑜𝑜

𝑥𝑥 = 0 𝑥𝑥 = 𝑎𝑎

• Transmission
2
𝐹𝐹 1
𝑇𝑇 = =
𝐴𝐴 𝑘𝑘 2 − 𝑘𝑘 ′2
1+ sin2 𝑘𝑘 ′ 𝑎𝑎
2𝑘𝑘𝑘𝑘𝑘

If 𝑘𝑘 ′ 𝑎𝑎 = 𝑛𝑛𝑛𝑛, T(E) = 0 T(E) = 1

𝑇𝑇 𝐸𝐸 = 1  Resonance
 Potential Barrier Simulation

• http://phet.colorado.edu/en/simulation/quantum-tunneling
 Real-World Examples

• Confinement potentials
• Scanning tunneling microscopy
 Real-world examples of
confinement potential

• Quantum dot

- Three-dimensional (3D) confinement

- “Particle in a box”
- Energy levels, if the quantum dot is modeled by a 3D infinite
potential well problem, are given as a straightforward extension
of the 1D infinite well problem:

ℏ2 (𝑚𝑚2 +𝑛𝑛2 +𝑙𝑙 2 )𝜋𝜋2

𝐸𝐸𝑚𝑚,𝑛𝑛,𝑙𝑙 =
2𝑚𝑚∗ 𝐿𝐿2
 Quantum Dot
Application of a quantum-confinement effect in displays
Nanosys.com

Bawendi group @ MIT

CREOL@ UCF
Nanosys.com
Real-world examples of confinement potential

• Quantum well

- Configuration in which a semiconductor

layer is sandwiched by other
semiconductor layers with larger band
gap can create a quantum well structure.

- Electrons are then confined in quasi-

two dimensional space.

- Useful in semiconductor lasers and

LEDs, etc.
Real-world examples of confinement potential

As the gate voltage is applied,

MOS (metal-oxide-semiconductor) device the potential profile changes
conduction
band edge

Workfunction 𝑉𝑉𝑔𝑔 = 0 𝑉𝑉𝑔𝑔

(Metal Gate)

Band
Offset
valence
band edge

“Electron gas” in MOS

inversion layer
• Electron gas in MOS
- Electrons become confined in the potential well of inversion layer which
an be approximated by a triangular.
 Application of tunneling :
scanning-tunneling microscopy (STM)
Wikipedia.org
Made by electrochemically etching a wire
made from tungsten, gold, etc.
The STM is a non-optical microscope
which employs principles of quantum
mechanics. An atomically sharp probe
(the tip) is moved over the surface of
the material under study, and a voltage
is applied between probe and the
surface. Depending on the voltage
electrons will "tunnel" (this is a
quantum-mechanical effect) or jump
from the tip to the surface (or vice-
versa depending on the polarity),
resulting in a weak electric current. The
size of this current is exponentially
dependent on the distance between
probe and the surface.
Wikipedia.org