0.

Prelude -- Development of
Classical Physics and Dark Clouds

(before 20th century)

1
 Classical Mechanics

Newton, Sir Isaac, PRS,

(1643 – 1727), English
physicist and
mathematician

Euler, Leonhard Lagrange, Joseph Louis Hamilton, William Rowan (1805 --

(1707 -- 1783), (1736 -- 1813), 1865),
Swiss Italian-French Irish mathematician and 2
mathematician. mathematician, astronomer astronomer.
 Classical Electrodynamics

Coulomb, Charles A Biot, Jean Baptiste (1 Ampere, Andre Faraday, Michael Lorentz, Hendrik A
ugustin (1736 – 1806) 774 --1862), French P Marie (1775 -- 1836), (1791 -- 1867), ntoon (1853 -- 1928)
, French physicist hysicist; French Physicist English Physicist , Dutch Physicist
Savart, Félix (1791 -- 1
841),
French Physicist

Maxwell, James Clerk (1831 – 1879), Scottish physicist 3

 Classical Thermodynamics

Dalton, John (1766 Carnot, Nicolas Joule, James Helmholtz, Hermann

-- 1844), British Léonard Sadi (1796 Prescott (1818 -- Clausius, Rudolf Juli
Ludwig Ferdinand von (1
chemist and -- 1832), 1889), British us Emanuel (1822 --
821 -- 1894), German phy 1888) , German math
physicist. French physicist. physicist. sicist and physician. ematical physicist.

Boltzmann, Ludwig, (1844 –

1906), Austrian physicist.

Thomson, William Maxwell, James

(Baron Kelvin) (182 Clerk (1831 –
4 - 1907), British p 1879), Scottish
hysicist and mathe physicist 4
matician.
 Classical Statistical Mechanics
Equal a priori probability postulate (Boltzmann)

Given an isolated system in equilibrium, it is found with equal

probability in each of its accessible microstates.

Canonical ensemble (isolated system)

Grandcanonical ensemble (opened system)

Boltzmann, Ludwig, (1844 –

1906), Austrian physicist.

Microcanonical ensemble
(independent system)

5
 Dark Clouds

Lord and Lady Kelvin at the Sir William Thomson William Thomson produced 70
coronation of King Edward working on a problem of patents in the U.K. from 1854
VII in 1902. science in 1890. to 1907.

“There is nothing new to be discovered in physics now.

All that remains is more and more precise measurement.” 6
 Dark Clouds
"Beauty and clearness of theory... Overshadowed by two clouds..."

Nineteenth-Century Clouds over the Dynamical Theory of Heat and Light

(27th April 1900, Lord Kelvin)

Michelson, Albert Morley, Edward

Einstein, Albert Planck, Max
Michelson-Morley Experiment (1887)

Ultraviolet catastrophy in blackbody radiation (before October, 1900)

7
I. Experiments and Ideas
Prior to Quantum Theory

(Before 1913)

8
 Radiation:
Blackbody Radiation and
Quanta of Energy

9
Planck (1858 -- 1947), German physicist.

Planck's law of black body

radiation (1900)

Planck’s assumption (1900): radiation of a given frequency ν could only be

emitted and absorbed in “quanta” of energy E=hν

10
 Radiation interaction with
matter: Photoelectric Effect
and Quanta of Light

11
1. In 1839, Alexandre Edmond Becquerel observe
d the photoelectric effect via an electrode in a con
ductive solution exposed to light.

2. In 1873, Willoughby Smith found that selenium i

s photoconductive.

3. In 1887, Heinrich Hertz made observations of the

1
photoelectric effect and of the production and rece me vk2  Ek  h  W
ption of electromagnetic (EM) waves. 2
4. In 1899, Joseph John Thomson (N) investigated In 1905, Albert Einstein (N)
ultraviolet light in Crookes tubes. proposed the well-known
Einstein's equation for
5. In 1901, Nikola Tesla received the U.S. Patent 68 photoelectric effect.
5957 (Apparatus for the Utilization of Radiant Ene
In 1916, Robert Andrews
rgy) that describes radiation charging and dischar
Millikan (N) finished a
ging conductors by "radiant energy".
decade-long experiment to
confirm Einstein’s
6. In 1902, Philipp von Lenard (N) observed the va
explanation of photoelectric
riation in electron energy with light frequency.
effect.
12
Atomic Structure

13
 Nuclear atom model (1911): Ernest Rutherford

Rutherford, Ernest, 1st Baron Rutherford of Nelson,

OM, PC, FRS (1871 -- 1937), New Zealand-English
nuclear physicist.

14
 Classical physics: atoms should collapse!
This means
an electron
should fall
into the
nucleus.

Classical Electrodynamics: charged

particles radiate EM energy New mechanics is
(photons) when their velocity
vector changes (e.g. they needed!
accelerate).

15
 Spectroscopy
Balmer, Johann
Jakob (1825 -- 1898), from n ≥ 3 to n = 2
Swiss mathematician
and an honorary
physicist.
Balmer series visible spectrum
(1885)
Balmer's formula (1885)

Rydberg formula for hydrogen

(1888)

Rydberg, Johannes Rydberg formula for all

Robert (1854 -- 1919),
Swedish physicist.
hydrogen-like atom (1888)

Bohr's formula (1913)

16
II. Old Quantum Theory

(1913 -- 1924)

17
 Bohr's model of atomic structure, 1913

The electron's orbital angular

momentum is quantized

Bohr, Niels Henrik David (1885 -- 1962), D

anish physicist.

The theory that electrons travel in discrete orbits around the atom's nucleus, with the chemical
properties of the element being largely determined by the number of electrons in each of the outer
orbits

The idea that an electron could drop from a higher-energy orbit to a lower one, emitting a photon
(light quantum) of discrete energy (this became the basis for quantum theory).

Much work on the Copenhagen interpretation of quantum mechanics.

The principle of complementarity: that items could be separately analyzed as having several
contradictory properties. 18
Bohr’s theory in 1 page

1 e2 mv 2
circular motion: 
4 0 r 2 r
quantization of angular momentum: mvn rn  nKh
2
1 2 1 e 2
 1  me 4 1
total energy: En  mvn    
2 4 0 rn  4 0  2 K h n
2 2 2

Quantum predictions must match classical results for large n

2
 1  me 4
freq. of radiation at n 1: h  En 1  En    3 2 2
 4 0  n K h
2
vn  1  me 4
freq. of classical circular motion:    
2 rn  4 0  n3 2 K 3h3

K  1/ (2 )
mvn rn  nh / (2 )  n
19
 Summary
Electron Transitions Failures of the Bohr Model

It fails to provide any understanding of why

certain spectral lines are brighter than others.
There is no mechanism for the calculation of
transition probabilities.

The Bohr model treats the electron as if it were

a miniature planet, with definite radius and
momentum. This is in direct violation of the
uncertainty principle which dictates that
position and momentum cannot be
simultaneously determined.

The Bohr model gives us a basic conceptual

model of electrons orbits and energies. The
precise details of spectra and charge
distribution must be left to quantum
mechanical calculations, as with the
Schrödinger equation.

20
Prince de Broglie gets his Ph.D.
de Broglie matter wave
hypothesis (1923):

All matter has a wave-like nature

(wave-particle duality) and that the
wavelength and momentum of a
particle are related by a simple
equation.

21
 Davisson-Germer Experiment (1927)

Davisson, Clinton Joseph (1881

-- 1958), American physicist

Germer, Lester Halbert (1896 – 19

71), American physicist
Electron has wave nature
(diffraction)!

22
 Later developments
• Born’s statistical interpretation of wavefunction
• Matrix mechanics (Heisenberg, Born, Jordan)
• Wave mechanics (Schroedinger)
• Uncertainty principle (Heisenberg)
• Relativistic QM (Dirac)
• Exclusion principle (Pauli)

23
 Birth of QM
• The necessity for quantum mechanics was thrust upon us by a
series of observations.
• The theory of QM developed over a period of 30 years, culminating
in 1925-27 with a set of postulates.
• QM cannot be deduced from pure mathematical or logical
reasoning.
• QM is not intuitive, because we don’t live in the world of electrons
and atoms.
• QM is based on observation. Like all science, it is subject to change
if inconsistencies with further observation are revealed.

24
 Fundamental postulates of QM
• How is the physical state described?
• How are physical observables represented?
• What are the results of measurement?
• How does the physical state evolve in time?

These postulates are fundamental, i.e., their explanation is beyond the scope
of the theory. The theory is rather concerned with the consequences of these
postulates.

25
 Goal of PHYS521 and 522
• We will focus on non-relativistic QM.
• Our goal is to understand the meaning of the postulates the theory
is based on, and how to operationally use the theory to calculate
properties of systems.
• The first semester will lay out the ground work and mathematical
structure, while the second will deal more with computation of real
problems.

26
Linear Algebra of Quantum Mechanics

27
The mathematical structure QM describes is a linear algebra of
operators acting on a vector space.

Under Dirac notation, we denote a vector using a “ket”:

v

The basic properties of vectors :

* c v is another vector
* v  w is another vector
* null vector: v  v  0
0 v 0

28
 A set of vectors 1 , 2 , ... , n are linear independent if
c1 1  c2 2  ...  cn n  0 implies c1  c2  ...  cn  0.

A vector space is n-demensional if

the maximum number of linearly independent vectors in the space is n.

A set of n linearly independent vectors in n-dimensional space is a basis

--- any vector can be written in a unique way as a sum over a basis:
n
v   vi i
i 1

Once the basis is chosen, a vector can be represented by a column vector:

 v1 
 
 v2 
 
  29
 vn 
A ket vector v is associated with a bra vector v in the dual space.
*
The inner product of two ket vectors v and w are w v  v w
The dual of c v is v c *.
The norm of v is defined as v  vv.
2 2 2
The Schwartz Inequality: w v v w .

Usually we require the basis to be orthonormal: i j   ij

A linearly independent set of basis vectors can be made orthonormal

using the Gram-Schmidt procedure.

Give an orthonormal basis  i  , and v   vi i ,

vi  i v

30
A linear operator  Aˆ takes any vector in a linear vector space to another vector
in that space: Aˆ v  v ' and satisfies: Aˆ  c v  c v   c v '  c v '
1 1 2 2 1 1 2 2

Identity operator I : I v  v for all v .

For a n-dimensional space with an orthonormal basis 1 , 2 , ..., n ,

the linear operator is completely determined by its action on the basis vectors,
and the identity operator can be express as:
n
I  i i
i 1

31
Give an orthonormal basis  i  , if Aˆ v  v ' , then vi '  Aij v j
where vi '  i v ' , vi  i v , Aij  i Aˆ j

Therefore the action of Aˆ is simply equivalent to matrix multiplication:

 v1 '   A11 A12  A1n  v1 
    
 v2 '    A21 A22  A2 n  v2 
         
    
 vn '   An1 An 2  Ann  vn 
and Aˆ can then be represented by an n  n matrix.

32
If Aˆ v  v ' , then v '  v Aˆ † . Aˆ † is called the adjoint of Aˆ .

Give an orthonormal basis  i  , like Aˆ , Aˆ † can also be represented by an n  n matrix

and the matrix elements of Aˆ and Aˆ † are related by
A 
†
ij
 A*ji

An operator equal to its adjoint (Aˆ  Aˆ † ), is called Hermitian.

An operator equal to minus its adjoint (Aˆ   Aˆ † ), is called anti-Hermitian.

An operator is unitary if Uˆ †Uˆ  1  UU

ˆ ˆ †.

33
Unitary operator possesses the following properties:

It preserves the norm of a vector: if v '  Uˆ v , then v '  v

It preserves the inner product: if v '  Uˆ v and w '  Uˆ w , then v ' w '  v w
It transforms one orthonormal basis in the space to another orthonormal basis.
Conversely, any transformation that takes one orthonormal basis to another must be unitary.

34
Eigenkets and Eigenvalues:

Aˆ ai  ai ai

Eigenvalues are roots to the characteristic polynomial

A11   A12  A1n

A21 A22    A2 n
det  A   I  
   
An1 An 2  Ann  

The set of eigenvalues of an operator satisfy:

n n

a   A
i 1
i
i 1
ii  Tr( A)
n

a
i 1
i  det( A) 35
Eigenkets and Eigenvalues of Hermitian Operators:

Aˆ ai  ai ai

All the eigenvalues are real.

Eigenkets belonging to different eigenvalues are orthogonal.
The complete eigenkets can form an orthonormal basis.
The operator can be written as Aˆ  n a a a .

i 1
i i i

36