Quantum Mechanics in

Chemistry
Chemistry 110A
Prof. C. William. McCurdy
2016 spring quarter

Syllabus is Posted on SmartSite

Text: We will use Donald A. McQuarrie and John D.
Simon, Physical Chemistry - A Molecular Approach
(University Science Books, 1997).
There is a solution manual available: Caveat emptor! It
contains errors and a few nonsensical explanations.
Minimum Prerequisites: Chem. 2C, one year of college
physics, and Math 16C or Math 21C. Having taken the
entire B.S. in Chemistry mathematics curriculum (21AD and 22A, 22AL (MatLab), and 22B. ) is better
Grading: The distribution of the points in the course
will be:
Homework
20%
Midterms (2)
each
20%
Final exam
40%

Week

Date

March 29 Role of quantum mechanics in Chemistry (Chap. 1 is background)

March 31 Chapter 2 Classical Wave Equation,
Superposition of solutions interference
April 5
Chapter 3 The Schrdinger Eq. and quantum interference,
Particle in a Box, separation of variables
April 7
Chapter 4 Principles and Postulates of Quantum Mechanics
April 12 Chapter 4 Hermitian operators, matrix elements
Uncertainty, Ehrenfests theorem, commutators
April 14 Chapter 5 Harmonic Oscillator + Rigid Rotor
Note Date
April 19 Chapter 5 Harmonic Oscillator + Rigid Rotor
April 21 Midquarter Exam on Principles of Quantum Mech-- in class
April 26 Chapter 6 Schrdinger equation for Hydrogen
atom and separation of angular from radial motion
April 28 Chapter 6 contDegeneracy, and symmetry in the H atom
May 3
Chapter 7 Approximation methods: The variational principle
May 5
Chapter 7 cont.
First order perturbation theory, examples
May 10
Chapter 8 Spin, Stern Gerlach experiment, beginning many-electron atoms
May 12
Slater determinants, Hartree-Fock approximation
May 17
Chapter 8 cont. Term Symbols, atomic excited states, Hunds rules
May 19
Chapter 9 Diatomic Molecules, Born Oppenheimer approx
Molecular Hamiltonians
Note Date
May 24
Midterm Exam on Atoms and approximations in class
May 26
Chapter 9 Molecular orbitals, H2+,
May 31
Chapter 9 Hartree-Fock & molecules, Bonding in first row diatomic
June 2
Electronic excited states of molecules

II
III
IV
V
VI
VII
VIII
IX
X

June 8

Topic

Final Exam 10:30 am Check date and time in last week of class

Note Date

Studying for this course

In the Chemistry curriculum this is the first course that
asks you to integrate what you learned in other
courses:
General Chemistry
Calculus and Linear Algebra
Physics

There are math and physics review sections in the

text -- use them if you have forgotten any of the skills
that are assumed in the text.
Read the text and do the homework problems
early. This subject is learned by doing -- not by
watching.

Mathematica, MATLAB, Python and the

Problem Sets
Mathematica, MATLAB or Python will be required for some
problems after week 1.
It is highly recommended that you use one of them frequently
to help check your algebra on homework problems.
Mathematica, MATLAB and Python examples will be posted
to help you improve your skills.
Mathematica Tutorial by Professor McCurdy will be
announced for an evening in the week of April 4. Needed
Skills:

Symbolic integration and differentiation

Line graphs: f(x), and plotting of surfaces: f(x,y)
Do and If statements, use of arrays
Eigenvalues and eigenvectors of matrices

Chapter 1: Why Quantum?

The Failures of Classical Mechanics
Blackbody Radiation This is important,
and we will look at it now.
You saw the others in Freshman
Chemistry:
Photoelectric Effect
Quantum interference -- wave properties of
particles
Hydrogen atom spectrum

We will just briefly review them today

Black Body Radiation

A cavity at thermal equilibrium at temperature T
What spectrum of electromagnetic radiation does it
emit?
An idealization of how any object characterized by
a temperature glows (emits radiation)

Where does the black body law come from?

Light consists of electromagnetic waves
obeying physics similar to mechanical waves

Classical modes of oscillation of a string. Each has a

different frequency, but can have any amount of energy.

Where does the black body law come from?

Modes of light oscillation in a cavity.
Light consists of electromagnetic waves
obeying physics similar to mechanical waves

Light modes have quantized energies

with n = 1, 2, 3 ! -- called photons

E = n h

Where does the black body law come from?

Number of modes
of frequency v

8
3
c

8
3
c

Average energy
of each mode

kB T
h /kBT

h e
h /kBT
1 e

Classical

Quantum
Boltzmann
distribution

Classical Thermodynamics gave the same energy to each mode

Quantum Mechanics gives a different mean energy to each mode

Black Body Radiation Law

The ultraviolet catastrophe of classical physics
Spectral radiation density [Energy/Vol/(unit of
frequency)] -- Planck distribution law
max =

hc
4.96511 kT

Classical mechanical distribution

8kT
( )d = 4 d

Key concept that leads

to Planck law

E = n h

8 hc
1
( )d = 5 hc/ kT
d
e
1
Equivalent distribution in terms of frequency:

8 h 3
( )d = 3 h / kT
d
c e
1

We see it every day

Distributions (like the Planck distribution)

A distribution, like the density (a mass
distribution), gives the relevant quantity only
when integrated over an interval or domain.

Mass =

density

(r) d r

Vol

Energy
between 1 and 2 =
Volume

( )d

From first problem set

c/4 times Planck distribution gives the distribution
of Radiated Power
(Watts/unit area/unit frequency)
3

c 8 h
(T )d =
d
3
h /kBT
4 c e
1
So integrating this distribution over all frequencies
gives

(T
)d

=
Radiated
Power/Area
(Watts/m
)

0

Photoelectric Effect--freshman
chemistry version
mv 2
Ekin =
= h
2
is the "work function"

Ekin = h h 0

In chemistry this phenomenon is called

photoionization and the work function
is called the ionization potential

Wave properties of particles

The De Broglie relation
Diffraction of electrons from a crystalline surface

h
=
p

Hydrogen Spectrum
Line spectra appear for all atoms in absorption and
emission.
The freshman chemistry story relates those
frequencies to transitions between discrete energy
levels given by the Bohr formula for hydrogen energy
levels.

h = E = E f Ei
Bohr formula

1 $1
1'
= & 2 2 ) 109680cm 1
% n1 n 2 (

Freshman chemistry
figures showing old
pictures of spectra
dont remotely reflect
todays spectroscopy
Those were pictures of
spectra taken with 1930s
technology.
We know the energy levels
of atoms to many
significant figures from
both experiment and
quantum theory
(From the NIST website)

Hydrogen Atom Transitions and Photoionization

RH
Ejected electron kinetic energy
En = 2
n

13.6 eV ionization energy

1 $1 1'
= & 2 2 )109680cm 1
% n1 n2 (

Correcting a false impression: The hydrogen atom absorbs

all frequencies corresponding to energies above 13.6 eV -NO discrete lines, as there are for lower frequencies
Photoionization
spectrum (photo
absorption) plotted
versus kinetic
energy of ejected
electron

E kin = h 13.6 eV

Remember the
photoelectric effect
same equation for ejected
electron Energy

Photoionization of an Atom Gives the

Binding Energies of the Atomic Orbitals
log-log
plot

X-ray photoionization -- for example

at the Advanced Light Source at the
Lawrence Berkeley Lab or Advanced
Photon Source at Argonne

For each type of atom we see

edges in the photoionization cross
section (probability) corresponding
to the energies of the atomic orbitals
that are occupied in the atom

The QM Roadmap of 110A

How simple 1D models are the basis of all chemical intuition
Schrdinger Equation
Postulates of QM

Particle in a box

Origin of discrete
energies

Translational
partition function
in statistical
mechanics

Harmonic Oscillator

Normal Mode
analysis

Rigid Rotor

Symmetric
+Asymmetric
Top Rotors

Blue = topics from 110A

Red = topics from 110B/C

One-electron atom

Approximation methods
Hartree Fock
Approximation

Vibrational/Rotational Spectra (IR

and microwave)

Bonding
Molecular orbitals

Electronic Spectra (Vis, UV and

X-ray)

Electronic Structure of
Polyatomic Molecules
Electronic States and
Molecular Potential
Curves

The history of early 20th century

science is NOT why we study QM
Bonding in molecules cannot be
understood without Quantum Mechanics.
No chemical spectroscopy could be
interpreted without Quantum Mechanics.

IR spectra: vibrational and

rotational transitions
From this spectrum: CO bond
distance in CO2 = 1.16, 16O is a
Boson (missing rotational lines)

Visible/UV spectra - electronic,

vibrational, rotational transitions
Electronic transition in I2 visible
spectrum

Time-dependent spectroscopy has been

invented using short pulsed lasers

Molecular Rotation: tens of picoseconds (10-12 s)

Molecular Vibration: tens of femtoseconds(10-15 s)
Electronic motion: order of tens to hundreds of
attoseconds (10-18 s)

Modern
Spectroscopy
in the time
domain:
femtosecond
chemistry

Femtosecond spectroscopy
to follow a reaction

Essential Mathematics
Simple concepts of complex variables are essential
Solutions of Schrdinger are frequently intrinsically
complex valued functions

Polar representation of a complex number

z = x + iy = re

r = z = x 2 + y2
cos = x / r = x / x 2 + y 2
sin = y / r = y / x 2 + y 2

Euler Identity and Complex Conjugation

Euler identity

Youll use it constantly as the basis of other simple identities

i +2 i

ei = cos + i sin

= ei

i=e

Complex conjugation

1 i /2
=e
= i
i

i /2

z = x + iy
z* = x iy

f (z)* means change the sign of i and

complex conjugate z wherever it appears in f (z)

for example :
f (z) = 5z 2 + iz + 2
2

f (z)* = 5( z* ) iz* + 2

Integrals of Complex Functions of a Real Variable

Same principles as integration of real functions, but keep
track of the complex quantities.

Simple example that will be used with the wave functions of the
hydrogen atom
f ( ) = ei
g( ) = e2i
2

What is

f ( )* g( )d ?

f ( )* g( )d =

i 2i
e
e d =

i
e
d =

i 2

e
i

= i(e2 i e0 ) = i(11) = 0

Basic Linear Algebra

Dot products of vectors appear with complex conjugation
N
in QM
X
uv =
ui v i
0 1
0 1
v1
u1
i=1
B v2 C
B u2 C
B C
C
N
X
v=B . C u=B
B
C
.
@ .. A
@ .. A
u v =
ui vi
i=1
vN
uN
A vector is normalized to one if
Two vectors are orthogonal if

u u = 1

u v =0

Eigenvalues and eigenvectors of matrices

A real symmetric (or Hermitian) matrix
0

M11
B M21
B
M=B .
@ ..

MN 1

M12
M22
..
.

M13
M23
..
.

MN 2

MN 3

M1N
M2N C
C
.. C
. A

MN N

has N eigenvectors and eigenvalues

Mvn =

n vn

and the eigenvalues are real numbers

the eigenvectors are orthogonal

Eigenvalues are the roots of an Nth order polynomial

Eigenvalues satisfy the secular equation (secular
determinant = 0)
det[M

M11
6 M21
6
I] = det 6
..
4
.

M12
M22
..
.

..
.

MN 2

MN 1

M1N
M2N
..
.
MN N

7
7
7=0
5

So they are the zeroes of an Nth order polynomial, e.g.

for a 2 x 2 they satisfy a quadratic equation

M11
M12
det
=0
M21
M22

(M11

)(M22

M12 M21 = 0