CHEM 351

Physical Chemistry II
Quantum Chemistry

1
 Spectroscopy
Microwave (Rotational)
Infrared (Vibrational)
– “Physical Chemistry”, 11th edition CH 7, Atkins
– “Fundamentals of Molecular Spectroscopy”, 4th
edition, Banwell & McCash

2
 Various notations are commonly used

~ 
Wavenumber  =
c
Pulsation  = 2
c 1
Wavelength = =~
 
h
Planck constant =
2
 The Electromagnetic Spectrum

• The basic!

MCWE (CH7F)
IR)(CH7E) UV-VIS (CH7D)
Quantum Chemistry
CH7D
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CH7E
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CH7F
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 Typical energies
Region Frequency/Hz NA h nf / ni

RF 7 4 mJ/mol
10 0.999998
MCWE 11 40 J/mol
10 0.984
IR 13 4 kJ/mol
10 0.202
UV-VIS 15 400 kJ/mol -70
10 3x10
X-RAY 1018 400 MJ/mol <10-99
6
 Molecular Energy Levels

The relative energy of the spacing between energy

levels for various types of transitions in a molecule are
in the order:

Vibrational Electronic
<< <<
Rotational
Transition Transition Transition

1-20 cm-1 2000-4000 cm-1 10000-50000 cm-1

Thus the various types of energy transitions occur in

different regions of the EMR spectrum and do not
overlap
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 Molecular Energy Levels

Molecules can have the following types of energy

1. Kinetic (due to motion)
2. Electronic (PE and KE of electrons)
3. Vibrational (oscillation of atoms in bonds)
4. Rotational

All except the KE are quantized

Emolecule = Erotational + Evibrational + Eelectronic

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 Molecular Energy Levels

Excited
Electronic
State

Vibrational
Rotational Energy
Energy Levels Levels

Ground
Electronic
State
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 Molecular Energy Levels

Radiation can be absorbed or emitted if the molecule

changes any of its energy states

Excited
Electroni
c State

Vibrational
Rotational Energy Levels
Energy
Levels

Ground
Electronic
State

Rotational Vibrational Electronic

Transition Transition Transition 10
 Molecular Energy Levels

Excited
Electroni
c State

Vibrational
Rotational Energy Levels
Energy
Levels

Ground
Electronic
State

Rotational Vibrational Electronic

Transition Transition Transition
1-20 cm-1 2000-4000 cm-1 10000-50000 cm-1

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Microwave Infrared UV-Visible
Basic Quantum theoretical approaches:
– Particle in a box
– Harmonic oscillator for vibration
– Rigid rotor for rotation
CHAPTER 7
Introduction to Quantum Theory:
7A The origin of quantum mechanics (classical
physics)

7A.1 Energy quantization

(a) Black-body radiation

7A.2 Wave-particle duality

(a) The particle character of electromagnetic radiation
(b) The wave character of particles
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CHAPTER 7
Introduction to Quantum Theory:
7A The origin of quantum mechanics (classical physics)

Question 1: How the classical mechanics has evolved into

quantum mechanics?

3 phenomena have led to 3 theories and 2 properties of

quantum particles

1. Black-body radiation, Planck theory, energy quantization

2. Photoelectric effects, Einstein theory, wave-particle duality
3. Electron diffraction, De-Broglie theory, wave-particle
duality
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 Classical Physics:
General Chemistry 1: Chapter 6
(sections 6.1, 6.2, and 6.4)
➢Particle properties (mechanics and dynamics in PHY 105)-
mass, velocity and acceleration
oElastic collision phenomena
o Kinetic and potential energy interchanges in Classical
Thermodynamics
➢Wave properties-wavelength, frequency and amplitude
o Constructive and destructive interference phenomena
o Harmonic oscillators
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Classical
Physics

Electromagnetic radiations : an oscillating electric and magnetic fields that

spreads through empty space or vacuum as a harmonic wave generated by the
accelerations of electric charge.
Harmonic wave, wave displacements that can be expressed as sine or cosine
functions
➢ Speed of light, c: the speed at which the electromagnetic wave travels = 3 x
108 m/s
➢ Wavelength, λ: the distance between two peaks of the wave = ? m
➢ Frequency, ν: the number of times per second at which wave displacement
at a fixed point returns to its original value in unit of Hz = ? s-1
λν =𝑐
19
 Classical Physics
Wavenumbers: reciprocal centimeters cm-1
1
ν෤ =
λ
Light in the classical physics: is an electromagnetic radiations that falls in the
visible region of the spectrum

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 7.A1 Energy quantization

Ultraviolet Catastrophe-1859: The result from the classical

description of black-body radiations (that energy and intensity are the
same)

zent colors and intensities

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 7.A1 Energy quantization

Black-body: A hot object

capable of absorbing
and emitting all
wavelengths of
electromagnetic
radiations uniformly.

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 7.A1 Energy quantization

➢ Black-body Radiations Experiment Heat a metal bar – it glows red – heated further- it glows
white, why?
▪ As the temperature is raised the wavelength of radiations is blue-shifted, why?
▪ As the temperature is raised the proportion of the blue-shifted radiations increased, why?

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7.A1 Energy quantization

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 7.A1 Energy quantization

➢ Max Planck: Energy of each electromagnetic oscillator is limited to discrete

values and cannot be varied arbitrarily (quantization of energy)

E = n hν n = 0, 1, 2, …
Where h is the Planck constant = 6.626 x 10-34 J s.

➢ Existence of invisible “packets’ of energy (Quanta of energy)

➢ Energy is determined by the frequency of each quantum
➢ Quantum of energy is hv and called a photon

25
 7.A1 Energy quantization
➢ Planck’s energy distribution:

8𝜋ℎ𝑐
𝜌(λ, 𝑇)=
λ5 (𝑒 ℎ𝑐/λ𝑘𝑇 −1)
Insert Figure 7.7

26
 7.1 Energy quantization
➢ Rayleigh-Jeans Law: all oscillators of the black body radiations (low and
high frequencies) are excited.

➢ Max Planck: The oscillators are excited only if they acquire an energy of at
least hν.
▪ Emitter of high frequency (short wavelength) can’t be excited by small
energy, regardless of the intensity (number of quanta)

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Summary of Planck Theory 1900

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29
 7A.2 Wave-particle duality

(a) Photoelectric effects -(Albert Einstein 1904)

Wave (electromagnetic radiations) behaves like a particle
(photon)

(b) Diffraction of electrons -(Louise de Broglie 1924)

Particle (electron) behaves like a wave

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7A.2 Wave-particle duality
(a) Particle character of electromagnetic radiation

Photoelectric effects: The ejection of electrons from

metals when they are exposed to ultraviolet radiation

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 7A.2 Wave-particle duality
(a) Particle character of electromagnetic radiation

32
7A.2 Wave-particle duality
(a) Particle character of electromagnetic radiation
Experimental Observation # 1

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7A.2 Wave-particle duality
(a) Particle character of electromagnetic radiation
Experimental Observation # 2

The kinetic energy of the ejected electrons increases linearly with

the frequency of the incident radiation.

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35
 7A.2 Wave-particle duality
(b) The wave character of particles

Diffraction of electrons experiments

Davisson and Germer: The constructive and destructive

interference caused by an object in the path of wave, leading to
enhanced or diminished intensity of the wave.

Thomson: Beam of electrons was diffracted when passed

through a thin gold film.

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De Broglie relation: Any particle, not only photons, travelling with a
linear momentum, should have a wavelength by the de-Broglie’s equation

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 Examples Sections 7A.1 and 7A.2
(Quantization and wave-particle duality)

Example 1: Calculate the number of photons emitted by a 100 W yellow

lamp (wavelength = 560 nm) in 0.1 seconds. Assume 100% efficiency
Hint. Power (P) = Energy (E)/time (Δt) with unit in W (J/s). Also, use Planck theory

Answer = 2.8 X 1020

Example 2: Estimate the wavelength of electrons that have been accelerated

through a potential difference ΔΦ of 40 V?
Hint. Assume the kinetic energy of the electrons (mass = 9.109 X 10-31 Kg) is equal to the
energy acquired by the electrons due to the potential difference, which is equal to the
charge of electron (e = 1.602 X 10-19 C) times the potential difference. Also, use De
Broglie’s relation.

Answer = 6.1 X 10-12

Also solve problems from Chapter 6 and Examples in Atkin Books

38
CHAPTER 7 - Quantum Theory:
7B Wavefunctions

Question 1: What are the most important concepts of quantum

mechanics? Why classical mechanics (classical physics) failed end of
19th century, when it was applied to particles as small as electrons?

1. Energy quantization
Particles have no arbitrary energy (energy is different from intensity)-Planck 1900

2. Wave-particle duality
Particles and wave concepts blend together-Einstein 1904

3. Uncertainty principle
Energy and position can’t be determined precisely-Heisenberg 1927

39
CHAPTER 7 - Quantum Theory:
7B Wavefunctions
7B.1 The Schrodinger equation
7C Operators and observable
7C.1(a) Eigenvalue equation
7D Translational motion
7D.2 Confined motion in one dimension
7E Vibrational motion
7E.1 The harmonic oscillator
7F Rotational motion
 CHAPTER 7 - Quantum Theory:
7B Wavefunctions
7B.1 The Schrodinger equation

Quantum mechanics: the concepts that treat the structures and

describe all properties of small, invisible particles like molecules,
atoms, and electrons-e.g. spectrum of hydrogen Bohr 1913

Notes: This is a new mechanics that acknowledges

the existence of quantization, wave-particle duality,
and uncertainly principle.

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 CHAPTER 7 - Quantum Theory:
Wavefunction: The mathematical representation of the
wave that in quantum mechanics replaces the classical
concepts of trajectory. It
is the solution of Schrodinger equation that describes all
properties of a system (Schrodinger 1926)

Schrodinger equation: Second order differential equation

used to calculate the wavefunction of a system.
 CHAPTER 7 - Quantum Theory:
7C Operators and observable
7C.1(a) Eigenvalue equation
Operators algebra: Mathematical techniques of quantum
mechanics (von Neumann 1932)
Question 2: What are the most important mathematical
operations in quantum mechanics?

1. Probability of finding a particle

2. Normalization
3. Eigen Value (observable)
4. Expectation (average) value (observable)
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Basic Quantum theoretical approaches:
– Particle in a box
– Harmonic oscillator for vibration
– Rigid rotor for rotation
CHAPTER 7 - Quantum Theory:
7D Translational motion
7D.2 Confined motion in one dimension

Particle in a box: a quantum model that is used to estimate

the energy for a particle of mass (m), which is confined to a
finite region of space between two impenetrable walls (1-D
box) under the influence of potential energy. The potential
energy is zero inside the box but rises abruptly to infinity at the
wall at x = 0 and x = L.
The time-independent Schrodinger equation:

Erwin Schrodinger 1926

CHAPTER 7 - Quantum Theory:
7E Vibrational motion
7E.1 The harmonic oscillator
7F Rotational motion
7F.1 Rotation in two dimension
CHAPTER 7 - Quantum Theory:
7E Vibrational motion
7E.1 The harmonic oscillator
Molecular Vibrations of CO2

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 Vibrational Energy of Diatomic Molecules

The bonds between atoms behave like

springs (classical mechanics)

The atoms vibrate approximately like a

harmonic oscillator, obeying Hooke’s
Law

F = -k(r – req)
k is the force constant

EPE = ½k(r – req)2

79
 Vibrational Spectrum of Diatomic Molecules

Interaction between EMR and the vibrational

energy of molecules can only occur if the bond is
polar and a change of dipole moment occurs
during oscillation.

Thus only polar bonds generate peaks in the

infrared spectrum of molecules.

Thus HCl, CO and HF absorb EMR and have an IR

80
spectrum but H2 and N2 do not.
 Vibrational States
• The energy levels are those of a quantum-mechanical oscillator.

• The frequency of a two-particle oscillator is

• Where the reduced mass is μ = m1m2 / (m1 + m2) and the spring constant is
κ.
 Various notations are commonly used

~ 
Wavenumber  =
c
Pulsation  = 2
c 1
Wavelength = =~
 
h
Planck constant =
2
 Example

A strong absorption of infrared radiation is

observed for 1H35Cl at 2991 cm-1.
a. Calculate the force constant, k, for this
molecule.
b. By what factor do you expect this frequency to
shift if deuterium is substituted for hydrogen in
this molecule? The force constant is unaffected
by this substitution.
 Solution
a. Solving for k,
hc h k Selection rule, we have Δn = ±1
E = hv = = and
 2 
2 (1.008)(34.969)
2

k = 4    = 4 2 (2.998 108 )(2991100)

c
2
1.66110− 27 = 516.3 N / m
  (35.977)
….(2.998x108)2….correct this!
b. The vibrational frequency for DCl is
lower by a substantial amount.
 HCl mH mcl ( mD + mC )  1.0078   36.983 
= =    = 0.717
 DCl
mD mcl ( mH + mC )  2.0140   35.977 
CHAPTER 7 - Quantum Theory:
7F Rotational motion
Electronic transitions Vibrational transitions
Rotational
transitions
Rotational Energy of a Diatomc Molecule

98
 Rotational Spectroscopy
In quantum mechanics, we have to change the
symbol for the angular momentum quantum
number from l to J.

Thus the dependence of the rotational energy

on the quantum number is given by
h2 h2
E= J (J + 1) = J (J + 1) = hcBJ (J + 1)
2ro2
8ro2

where rotational constant is

moments of inertia, I=mr2
 Rotational Energy of a Diatomic Molecule

Rotational energy is quantized

E = J(J + 1)B J=0,1,2,...
EMR will only be absorbed by polar molecules
e.g. HCl & CO absorb EMR but not H2 and N2
The electrical molecular dipole interacts with the fluctuating electric
field of the EMR wave
Only certain transition are allowed J = 1

12B
Rotational Microwave Spectrum

6B
2B
0 2B 4B 6B ? 105
 Rotational Spectroscopy
To excite various transitions consistent with the
selection rule, we have J = J final − J initial = +1
 Example

Because of the very high precision of frequency

measurements, bond lengths can be determined
with a correspondingly high precision, as
illustrated in this example. From the rotational
microwave spectrum of 1H35Cl, we find that
B=10.59342cm-1. Given that the masses of 1H
and 35Cl are 1.0078250 and 34.9688527 amu,
respectively, determine the bond length of the
1H Cl molecule.
35
 Solution

We have

h
B=
8 2  cr02
h 6.6260755 10−34
r0 = =
8  cB 2  (1.0078250 )( 34.9688527 ) 
2

8 c   (1.66054  10 −27
) (10.59342 )
 1.0078250 + 34.9688527 
= 1.274553 10−10 m
Exam 3
Vibration and Rotation Combined
 Vibration and Rotation Combined
• It is possible to excite the rotational and vibrational modes
simultaneously.
• Total energy of simple vibration-rotation system:
Morse Potential
It is a better approximation for the vibrational structure of the molecule than
the quantum harmonic oscillator because it explicitly includes the effects of
bond breaking, such as the existence of unbound states.

113
 Anharmonicity
• Deviations due to
anharmonicity
Vv Harmonic become more clear
oscillator
at
Anharmonic – higher energy levels
oscillator
(v), and
2
1 – larger x = r – re
0 values that
r0 correspond to
Bond distance
dissociation.
114
 Anharmonicity
 An simple analytical expression, called the Morse potential, represents the main features of
the real potential for a molecule:
- close to the minimum potential of depth De, the potential is close to be harmonic.
- for large displacement, the potential represents the bond dissociation

V ( x) = De [1 − e − ( x − xe ) ]2

➔ The Schrödinger equation can be solved with the Morse

potential and the permitted energy levels are:

1  ( hv ) 
2 2
 1
En = hv  n +  − n+ 
 2  4 De  2
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