Welcome to CH441:

Physical Chemistry II,

Quantum Mechanics v

Monday, January 8, 2024

Course Overview
Course assignments:
 Course assignments:
• Weekly quizzes: quizzes (30 min) taken on Canvas, available from Saturday 8 am to Monday
11:59 pm. Each week apart from week 1, 3, 5 and 8 (Syllabus quiz and Midterm/Quest
weeks).You have three attempts to take each quiz, but maximum grade is lowered for
subsequent attempts!
• Homework: Homework problems are taken from the textbook and are due 11:59 pm on
Sundays via Canvas.
 Canvas quiz policy
• These quizzes are open book and taken at home
• Calculators are allowed (no Graphing Calculator)
• You will be asked to upload a picture showing your work
• We discourage working together. Note that people in general will have slightly different
questions and questions might appear in different order, so working together won’t be of
much help and might confuse you.
• No “Homework Help” websites like Chegg.
 Course assignments:
• Quests: 3 longer, in class quizzes, 50 min, week 3, 5 and 8. Fridays during class time. These
are not open book, but you will receive a sheet with important formulas you might need.
Only your best two quests count.
• Quest reflections: Writing assignments after each Quest. Correct your mistakes and reflect
on how to improve your learning strategies.
• Final exam: In exam week, in-person, Thursday 21st March, 2:00pm. 110 minutes. Not open-
book, but you will have a formula sheet (non-Graphing calculator allowed)
• Syllabus quiz: No quiz in Week 1, instead we have the Syllabus quiz on Canvas. Answer
questions about the syllabus to receive 5 points.You can take this quiz an unlimited
number of times (This is the only quiz for which that is true)
• In class-quizzes: There will be frequent, short, in class exercises that you submit at the end
of class.
 Weekly tasks

• Weekly tasks are displayed on Canvas page.

• Attend class (classes will feature regular in-class quizzes for points)
• Read assigned textbook chapters
• Watch supplementary videos
 Getting Help
• Office hours: Come to my office hours (W 12-1pm LPSC 273, T 4-5 pm on Zoom) or my
TA’s office hours (time TBD) if you have any questions regarding the course.
• Contact details of TA’s and first points of contact for quizzes/homework will be posted on
Canvas early this week
• Informal Recitations: Run by TA’s, held in weeks that have Quests. Attendance is voluntary
(but there are bonus points on offer).
• Discussion boards: Each week has a dedicated discussion page on Canvas where you can
ask questions
Questions?
Why Quantum Mechanics in Chemistry?
 Quantum Mechanics in Chemistry
Periodic table Bonding

Spectroscopy

Cyclohexane
Benzene
Acetone
Strength (arb. units)
!"#$%&'&&

2 2.2 2.4 2.6 2.8 3 3.2

Energy (eV)
 Quantum mechanics is extremely successful!

“The underlying physical laws necessary for the mathematical theory

of a large part of physics and the whole of chemistry
are thus completely known, … “

Paul Dirac, Proc. Royal Soc. Vol 123, 792 (1929)

h = Planck’s Constant
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h @
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Ĥ =i = Wavefunction
Paul Dirac 2⇡ @t
Ĥ = Hamiltonian Operator
 But: Quantum Mechanics is hard!

“The underlying physical laws necessary for the mathematical theory

of a large part of physics and the whole of chemistry
are thus completely known, and the difficulty is only that the exact
application of these laws leads to equations much too complicated to
be soluble. “

Paul Dirac, Proc. Royal Soc. Vol 123, 792 (1929)

h = Planck’s Constant
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Ĥ =i = Wavefunction
Paul Dirac 2⇡ @t
Ĥ = Hamiltonian Operator
 Computing the many-electron wavefunction

• We can use computers to solve the equations of quantum mechanics

exactly.
• But: Solutions scale exponentially with number of electrons.

Carbon dioxide

16 valence electrons
 Computing the many-electron wavefunction

• We can use computers to solve the equations of quantum mechanics

exactly.
• But: Solutions scale exponentially with number of electrons.

Carbon dioxide Intel i7 core Caffeine molecule

16 valence electrons 1 hour 74 valence electrons

calculation
time
 Computing the many-electron wavefunction

• We can use computers to solve the equations of quantum mechanics

exactly.
• But: Solutions scale exponentially with number of electrons.
• Exact solutions to even small molecules are impossible
Oak Ridge National Lab
Summit Supercomputer
Carbon dioxide Intel i7 core Caffeine molecule 26 million times faster

16 valence electrons 1 hour 74 valence electrons

calculation
time
 Computing the many-electron wavefunction

• We can use computers to solve the equations of quantum mechanics

exactly.
• But: Solutions scale exponentially with number of electrons.
• Exact solutions to even small molecules are impossible
Oak Ridge National Lab
Summit Supercomputer
Carbon dioxide Intel i7 core Caffeine molecule 26 million times faster

16 valence electrons 1 hour 74 valence electrons Approx. 5000x the age

calculation of the universe
time
 What you will do in this course:

• Learn the basic rules of Quantum Mechanics (Written in the language of

mathematics à Operators, eigenvalues, probabilities etc.)
• Learn how to solve the equations of quantum mechanics for simple model
systems

• Learn how to apply the concepts and model systems to atoms, molecules and
molecular spectroscopy

Figs. Taken from chem.libretexts.org

Questions?
Lecture 1: Why Classical Physics is wrong
 Lecture 1: Why Classical Physics is wrong

Historical context
• In the mid- 19th century, Physics seemed essentially complete
• Most natural phenomena very well described by Classical Mechanics (Newton),
Thermodynamics (Gibbs, Lord Kelvin, Carnot), Electromagnetism (Maxwell)
 Lecture 1: Why Classical Physics is wrong

Historical context
• In the mid- 19th century, Physics seemed essentially complete
• Most natural phenomena very well described by Classical Mechanics (Newton),
Thermodynamics (Gibbs, Lord Kelvin, Carnot), Electromagnetism (Maxwell)

• Albert A. Michelson “… it seems probable that most of the grand underlying principles
have been firmly established … An eminent physicist remarked that the future truths of
physical science are to be looked for in the sixth place of decimals.”

• But: Late 19th to early 20th century, some “issues” arose.

 Light is a particle: The photoelectric effect
Light is incident on a metal plate. Light can give energy to the electrons and knock
them loose. What happens if we vary the intensity and frequency (color) of the
light?

Fig taken from: https://en.wikipedia.org/wiki/Photoelectric_effect

 Light is a particle: The photoelectric effect
Light is incident on a metal plate. Light can give energy to the electrons and knock
them loose. What happens if we vary the intensity and frequency (color) of the
light?

Classical picture:
• Electrons can absorb energy carried
by EM wave
• Energy carried is proportional to
intensity of light, so increased
intensity à increased emission of
electrons and increased kinetic
energy of emitted electrons

Fig taken from: https://en.wikipedia.org/wiki/Photoelectric_effect

 Light is a particle: The photoelectric effect
Light is incident on a metal plate. Light can give energy to the electrons and knock
them loose. What happens if we vary the intensity and frequency (color) of the
light?

Classical picture: Actual observation

• Electrons can absorb energy carried
by EM wave
• Energy carried is proportional to
intensity of light, so increased
intensity à increased emission of
electrons and increased kinetic
energy of emitted electrons
• For light below a given frequency, no
electrons emitted no matter the
intensity
• Once frequency is increased,
electrons are emitted and their
kinetic energy varies linearly with
the frequency of incident light
• Higher intensity at high frequency
à more electrons emitted but no
increase in kinetic energy!

Fig taken from: https://en.wikipedia.org/wiki/Photoelectric_effect

 Light is a particle: The photoelectric effect
Interpretation:
• Light is made up of particles (photons) each carrying an amount of energy
proportional to the frequency

E = h⌫
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• Photons hit electrons and transfer their energy, but a certain minimum amount
of energy is needed for the electrons to break free (Work function, dependent
on the material).
• Excess energy given to the electron is converted into kinetic energy

1
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KE = me v 2 = h⌫
2

The work function of a metal is 2.3 eV and the incident light has a frequency of 6.0x1014 Hz.
What is the speed of the ejected electron?
Fig taken from: https://en.wikipedia.org/wiki/Photoelectric_effect
 Electrons are waves: The double-slit experiment

• Thomas Young’s double-slit experiment

with electrons (Davisson & Germer 1927)
• If electrons pass through the double-slit, an
interference pattern is formed à Wavelike
behavior

Picture taken from: https://en.wikipedia.org/wiki/Double-slit_experiment#/media/File:Double-slit.svg

 Electrons are waves: The double-slit experiment

• Thomas Young’s double-slit experiment

with electrons (Davisson & Germer 1927)
• If electrons pass through the double-slit, an
interference pattern is formed à Wavelike
behavior
• Pattern persists at low intensity
à true for single electrons!
• Impact position on screen for every single
electron is fundamentally random.

• Which slit does the electron pass through?

Copenhagen interpretation: Both!

Picture taken from: https://en.wikipedia.org/wiki/Double-slit_experiment#/media/File:Double-slit.svg

 All particles are waves: The de-Broglie relation
De-Broglie showed that all particles with mass behave as waves also and that the effective wavelength can be
calculated. How?

hc
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Einstein (Photoelectric effect): Photons have energies given by E = h⌫ =

Einstein (Relativity): photons have an effective relativistic mass E = mc2
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 All particles are waves: The de-Broglie relation
De-Broglie showed that all particles with mass behave as waves also and that the effective wavelength can be
calculated. How?

hc
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Einstein (Photoelectric effect): Photons have energies given by E = h⌫ =

Einstein (Relativity): photons have an effective relativistic mass E = mc2
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2
Combining equations: = mc ! = mc = p

à Photons are massless particles (travelling at speed of light) but have momentum!

Image credit: Josh Spradling/The Planetary society

 All particles are waves: The de-Broglie relation
De-Broglie showed that all particles with mass behave as waves also and that the effective wavelength can be
calculated. How?

hc
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Einstein (Photoelectric effect): Photons have energies given by E = h⌫ =

Einstein (Relativity): photons have an effective relativistic mass E = mc2
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hc h
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2
Combining equations: = mc ! = mc = p

à Photons are massless particles (travelling at speed of light) but have momentum!

De-Broglie (By analogy): Extend the equation to particles with mass travelling slower than light

h h h
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= p = mv ! = =
p mv

Image credit: Josh Spradling/The Planetary society

 The Bohr Atom: How is it stable?

• Emission spectra from atoms have distinct spectral

lines
• Only transitions of specific energies are possible
• Bohr Model is a simple model to explain this
phenomenon
• Electrons are thought to only exist on specific orbits
around a nucleus
 The Bohr Atom: How is it stable?

• Emission spectra from atoms have distinct spectral

lines
• Only transitions of specific energies are possible
• Bohr Model is a simple model to explain this
phenomenon
• Electrons are thought to only exist on specific orbits
around a nucleus

But: Maxwell tells us an accelerated charge

emits EM waves
THANK YOU v