Introduction to Quantum Chemistry

Why Quantum Chemistry?

There are many studies in the field of chemistry

Examples:

Chemical reaction Molecular spectroscopy

What is the role of quantum chemistry?

 Chemical Reaction

Explaining the reaction mechanism May be explained from

chemical bonding and orbitals
Example: catalytic reaction

Concept in quantum chemistry

L. Lv. et al., Organometallics, 32, 3837 (2013).
Involving many elementary process
 Spectroscopy

In toluene

R.A. Alder et al., Inorg. Chem., 56, 8718 (2017).

Fluorescence is greatly affected by the structure and solvent. Why? By employing

quantum chemical methods we can answer the questions.

In the end, experimentalists are helped by the insight from quantum chemistry knowledge
 Quantum chemistry: where to start?

Universe visible to us is usually called macroscopic universe.

The laws governing macroscopic universe is the classical (

Newtonian) mechanics.

“Unfortunately” the microscopic universe has totally different

physical laws. The laws governing microscopic level is called
quantum mechanics

We will see later at what condition at we have to use quantum mechanics

 Classical Mechanics
v

0 x

Quiz :

1. Other than the written above, what physical quantities does

that body have?
2. Suppose that you track the movement of above body in t
(time). Express the position at t!
3. How many possibility of (kinetic) energy value does above
system have? Suppose the velocity varies from v0 to vmax
 Classical Mechanics
v

0 x

Answers :

1. Momentum and kinetic energy

2. x = vt
3. There are infinity possibility of kinetic energy value between v0
to vmax
 Classical Mechanics

• Predict position (and momentum) precisely. (Answer

2)
• Allow continuous energy and generally observable
quantity. (Answer 3)

Classical motion

Translation Rotation Vibration

Black-body Radiation

Otto Lummer experiment ca. 1890

Hoffmann, 2000, Physikalische Blätter 56, 43

• A hot object emits radiation

• Perfect absorber = Perfect emitter
Black-body Radiation

Experimental results

dE
=r
5000 K
dl
r

4000 K

3000 K

0 500 1000 1500 2000

l (nm)
Black-body Radiation

Rayleigh-Jeans’ Law
Derived from classical
mechanics and
5000 K
thermodynamics
8p kT
r

r=
4000 K
l 4

3000 K

0 500 1000 1500 2000

l (nm)

Ultraviolet catastrophe !!
Black-body Radiation

Max Planck came with ideas

Planck’s Law
• EM waves are
considered as
5000 K oscillator
• E = nhn with n = 0,
1, 2, …
r

8p hc exp(- hc l kT )
4000 K
r= 5
3000 K l 1- exp(- hc
l kT )
0 500 1000 1500 2000
l (nm)

Reproduces the experimental curves !!

Heat capacity

• Dulong and Petit discovered that the heat capacity of any solid is
approximately 25 J/mol K

• The mean energy of atom in solid as it oscillates about its original

position is kT. For 3 degree of freedom, the energy is 3kT. Thus, for
NA atoms, the total energy becomes

U = 3N A kT = 3RT
• From the definition of heat capacity
dU
CV = = 3R
dT
• Agrees with Dulong and Petit experiment
Heat capacity

• From experimental results, the heat capacity tended towards to zero as

T0
• Einstein implemented the idea of Planck that the atom can be
considered as oscillator with single frequency
4

3.5 Dulong-Petit value

exp(q )
3
q T
2.5
CV = 3R( ) 2

T (1- exp(q ))2

Cv/R

1.5
T
1

0.5

0
0 0.5 1 1.5 2 2.5 3
T/q

• This is not the best approximation, but the discussion are going to the
right direction
Photoelectric effect

Discovered by Hertz

Ek = hv - f

h
Proof that light has momentum p=
l
Compton scattering

Due to conservation of kinetic energy and momentum, the scattered

photon has longer wavelength

h Where does the momentum come from ?

l f - li = (1- cosq )
mec
Atomic Hydrogen Spectra

Balmer empirical
formula
æ n2 ö
l = 364.506 ç 2 ÷
èn - 4ø

Generalization by
Rydberg

1 æ1 1 ö
= RH ç 2 - 2 ÷
l èn m ø
Still no theoretical explanation
The Duality of Matter

de Broglie relation

h
l=
p

Experimentally proven by
Davison-Germer (1927)

Proof that electron has wave property

Foundation of Quantum Mechanics

1. The state of a system is fully described by a function Y(r1, r2, . . .

, t).
• Recall de Broglie hypothesis
• The function contains any information about the particle(s)

1. The wavefunction must be continuous, differentiable, and

having finite value
2. The probability that a particle will be found in the volume
element dt at the point r is proportional to |Y(r)|dt.
Foundation of Quantum Mechanics

4. Every observables have mathematical representation

• These are the most important operators

x Þ x̂ º x ´

4. The form of time dependent Schrödinger equation

4. It is impossible to “measure” momentum and position

simultaneously with accurate precision
 Homework
• Find the application of the wave characteristic
of electron in chemistry.

• Reading assignment:
– Matrix
– Second order differential equation
– Eigenvalues and eigenfunctions