Winter 2013
Chem 356: Introductory Quantum Mechanics
Introduction to Quantum Mechanics: Syllabus ............................................................................................ 2
Introduction and History ............................................................................................................................... 3
Introduction to Quantum Mechanics ....................................................................................................... 3
Historical Background ............................................................................................................................... 4
A little digression on relativity theory....................................................................................................... 5
Introduction to Quantum Mechanics: Syllabus
Lectures:
Tutorials:
Website:
MWF
12:30 – 1:20 PHY 313
Friday
1:30 – 2:20 RCH 306
science.uwaterloo.ca/~nooijen
Grading:
20%
30%
50%
Assignments (Biweekly)
Midterm
Final Exam
Book: Quantum Chemistry 2nd Ed. By Donald A. McQuarrie
ISBN: 978-1-8913890-50-4
Problems and Solutions for McQuarrie’s Quantum Chemistry 2nd Ed. By Helen O.
Leung, Mark D. Marshall
ISBN: 9781891389528
*Lecture notes, to be provided
Some Fridays, we will do MathCad sessions and use computers to solve problems
For Midterm and Exam: you may bring a summary sheet (must write yourself however)
 Website:
To be enabled
 Lectures will focus on concepts, this can be somewhat abstract
 Tutorials:
You ask questions
 Solving Problems (sometimes extended problems): digest material, learn by practice
Introduction to Quantum Mechanics: Syllabus
2
Winter 2013
Chem 356: Introductory Quantum Mechanics
Introduction and History
Introduction to Quantum Mechanics
Quantum Mechanics:
fundamental theory of chemistry, together with statistical
mechanics (Chem 350) forms the microscopic theories of matter
Very few fundamental postulates derive all the rest. Everything we derive (correctly) should be
possible to be confirmed by experiment (Popper, a philosopher of science).
Today: Quantum Chemistry programs (eg. Gaussian) are very powerful tools to obtain
-
Molecular structure
Spectroscopic data, IR, NMR, CD, UV-vis, Resonance Raman
Thermochemical data  H,  G, S
Combine with molecular simulations
-
Properties of liquids
 G for complicated reactions
Kinetics, reaction rates
In quantum mechanics, the equations are simple, BUT hard to solve
 Huge effort to develop software that can solve equations efficiently
To be expected:
Simple equation “H  = E  ” describes bewildering set of microscopic phenomena
The concepts underlying Quantum Mechanics are strange, puzzling, even today
So how do we deal with and study, “simple equations”, “difficult solutions” yet “funny
concepts”?
→ study model problems:
- ‘easy’ solution
- Insight into solution
- Phenomenological rule
Quantum Mechanics is old by now, started seriously in 1926
Introduction and History
3
Winter 2013
Chem 356: Introductory Quantum Mechanics
Current Frontiers / Applications include
 Quantum Computing (exploiting the weirdness)
 Nanotechnology : Make materials that start to ‘use’ quantum mechanics
 Solid state devices (computer hardware, based on quantum mechanics)
 Lasers (quantum properties of light
Our focus will be Quantum Mechanics as the fundamental theory of chemistry.
Historical Background
(Classical) Physics around 1900
- Newtonian mechanics, Hamilton/Lagrange formations
- Maxwell equations, optics, electron magnetism
- Thermodynamics:
o Heat, work, energy, entropy
- Statistical Mechanics
o Boltzmann/Gibbs
Power of theoretical description: Derive equations from the fundamental theory. Predicted
phenomena should be verified experimentally and conversely
Any (reproducible) experimental fact that does not fit the theory is a disaster, and
theory would not be universally valid; would need a change….
→ But in practice our theories (fairly simple, really) work very well (so far so good)
In 1900, most people thought everything is understood, just dotting the I’s, as far as theory
goes
Things that did not fall into place
a. Velocity of light is constant
b. Gravitational mass = inertial mass
 special and general theory of relativity (Einstein)
c. Black body radiation (Planck)
Introduction and History
4
Winter 2013
Chem 356: Introductory Quantum Mechanics
d. Specific heat of solids (Einstein)
e. Photoelectric effect (Einstein)
f. Atomic spectra (Bohr)
..understanding chemistry!
Quantum mechanics!
Other new phenomena
a.
b.
c.
d.
X-rays (Roentgen)
Radioactivity (Becquerel, Curie)
Super-conductivity, Super-fluidity (Kamerling Onnes)
Discovery of electron 1898 (Thompson), nucleus 1911 (Rutherford)
Something MORE than just ‘dotting the i’s’!!
A little digression on relativity theory
(A prime example of logical thought)
Situation:
Go back to kids time, you are biking to the soccer field and throw a ball in the air with
both hands. (no hands to steer!)
Do you:
Throw the ball slightly forward (anticipating where you will be)?
OR
Throw the ball straight up as if you were not cycling as all?
OR
Throw the ball backwards?
What is the answer?
Let’s change the question.
You are in a steady moving train. How do you throw?
You are running. How do you throw?
Answer: We should throw straight up.
WHY?
Introduction and History
5
Winter 2013
Chem 356: Introductory Quantum Mechanics
Because the ball already has the velocity in the forward direction, we should throw straight up.
Let’s Draw a Picture
If you toss a bottle from a moving car, it will fly with huge velocity (of the car). Velocity
depends on perspective….But…
this is not true for light!
→ the velocity of light is vacuum is constant, independent of perspective.
What does this mean? Before we can answer this, let us consider the ball a bit
more.
Question: if the boy on the bicycle, and the on the ground, measure the time of flight, do they
get equal answers? Yes.
Questions & Answers regarding ball on train (slow)
From the boy on bicycle/train perspective:
the distance travelled by the ball, 2h
the (average) velocity of the ball, v y
time of flight, t
From the ground’s perspective:
Introduction and History
6
Winter 2013
Chem 356: Introductory Quantum Mechanics
distance travelled is longer 2h  t  vx
the (average) velocity of the ball,
v y 2  vx 2
time: the same t
Angle of throwing the ball:
o Straight from biking perspective
o Angled from ground perspective
Now shine a flashlight to a (far away) mirror, on a moving train
Speed of light is c always
(l  l )
t  
c
Observation: My own light (standing still) bounces back quicker than light on moving train.
For the same reason: boy (on train) says his light has returned before mine!
*note:
Introduction and History
7
Winter 2013
Chem 356: Introductory Quantum Mechanics
It would also take some time to observe the distant event. This can be taken into
account and corrected for. The math involved is a bit involved, no need for our purpose.
It is a consequence of the constancy of light that time is not absolute. Like distance which
depends on perspective, time duration also depends on perspective.
The detailed equations of special relativity are not so hard to derive.
The consequences are hard to accept, and it is pretty hard to get an intuitive feel for it.
Another consequence/Example.
c = signal velocity
(eg. Velocity of mail)
→ For regular mail: world traveler sends postcards from Honolulu, New York, Tokyo: they
might all arrive at the same time
Compare receiving 3 phone calls from the same person at the same time: One from Honolulu,
one from New York, one from Tokyo
Cannot happen because we cannot travel faster than the speed of light c .
Introduction and History
8