Focus 7: Quantum Theory

Text Book: Elements of Physical

Chemistry, Peter Atkins and Julio
de Paula, International Edition
 Topic 7A: The emergence of
Quantum Theory
• Classical Mechanics:
• Particles have definite trajectory, specified
locations and momenta at each instant.
• The translational, rotational and vibrational
motion is excited to any energy.
• Quantum Mechanics:
• Failure of classical mechanics to explain the
observed properties at molecular or atomic
dimensions led to emergence of Quantum
theory
The Electromagnetic Spectrum

c = νλ
The Electromagnetic Spectrum:
400 nm- 800 nm
The Electromagnetic Spectrum:
Color Wheel

Copyright © 2009 Royal Society of Chemistry www.rsc.org

 The evidence for discrete
energies
• An example of Atomic emission spectrum
of excited Fe atoms
 The evidence for discrete
energies
• An example of molecular absorption
spectrum of SO2 molecules.
The discrete energy levels in atoms or
molecules
• The energy of ‘internal modes’ of motion of
atoms or molecules (electronic excitation,
vibration and rotation) are confined to
discrete values.
• The energy can be discarded or absorbed
only in packets, as atoms or molecules jump
between allowed states.
• The frequency of the radiation is related to
the energy difference between initial and final
states.
 The evidence for discrete
energies
• Discrete energy levels account for
emission spectra from molecules or atoms

∆𝑬 = 𝒉𝝂: 𝑩𝒐𝒉𝒓
𝒇𝒓𝒆𝒒𝒖𝒆𝒏𝒄𝒚 condition
 Photoelectric Effect: Particle
nature of electromagnetic
radiation
• Electrons are ejected only if the frequency
exceeds a threshold value characteristic of
the metal.
• The kinetic energy of the ejected electrons
varies linearly with the frequency of the
incident radiation. (discovered by Albert
Einstein)
𝑬𝒌 = 𝒉𝝂 − 𝝓
 Photoelectric Effect
Energy of a photon = 𝒉𝝂

𝑬𝒌 = 𝒉𝝂 − 𝝓 ∶ 𝒉 𝐢𝐬 𝐭𝐡𝐞 𝐏𝐥𝐚𝐧𝐜𝐤 ′ 𝐬 𝐜𝐨𝐧𝐬𝐭𝐚𝐧𝐭,

𝝓 is the work function, 𝑬𝒌 is the kinetic energy
 Photoelectric Effect
• Bound electron, free stationary electron,
photoelectron
 Photoelectric Effect
• When 𝒉𝝂 < φ, can photoelectric effect occur?
 No electrons are ejected, regardless of the
intensity.
• How can photoelectric effect be an evidence for
particle nature of electromagnetic radiation?
 Energy transfer between photons and electrons:
electrons are released from metal with a net
kinetic energy, if 𝒉𝝂 > φ.
• What do you mean by work function of a metal?
 The minimum energy needed to remove an
electron from the metal and it is the analogue of
ionization energy of an atom.
Photoelectric Effect: Example
• Problem: A photon of radiation λ = 305 nm
ejects an electron from a metal with Ek =
1.77 eV. Calculate the threshold frequency
for photo ejection of the radiation to be
able to remove the electron from the
metal.
𝑇ℎ𝑟𝑒𝑠ℎ𝑜𝑙𝑑 𝑓𝑟𝑒𝑞. :
𝜙 (𝑕𝑐 𝜆);𝐸𝑘 𝑐 𝐸𝑘
𝜈𝑚𝑖𝑛 = = = − ≅ 5.6 × 1014 /𝑠
𝑕 𝑕 𝜆 𝑕
 Diffraction: Wave nature of
electromagnetic radiation
• Davisson-Germer experiment
 Diffraction: Wave nature of
electromagnetic radiation
• Diffraction occurs when the dimensions of the
object are comparable to the wavelength of
the radiation.
• de Broglie relation: for an electron
accelerated through a potential:
𝒉 𝒉
𝝀= =
𝒑 (𝟐𝒎𝒆 𝒆𝑽)𝟏/𝟐
• Example Problem: Estimate the wavelength
of electrons that have been accelerated from
rest through a potential difference of 1.00 kV
de Broglie relation: λ vs p
 7B: The dynamics of
microscopic systems
• Quantum Mechanics: Microscopic systems
(atoms, molecules and subatomic
particles): wavefunction and probability
of finding the particle
CLASSICAL OBJECT

SUBATOMIC
PARTICLE
 The Schrödinger Equation
2 2
ℏ 𝑑 𝜓
− + 𝑉 𝑥 𝜓 = 𝐸𝜓
2𝑚 𝑑𝑥 2
• Kinetic energy × Ψ + Potential energy × Ψ =
Total energy × Ψ
• Where Ψ is the wavefunction that contains all
dynamical information about the state of a system,
V(x) is the potential energy, and E is the total
energy of the system. ℏ = h/2π
• 𝑯𝝍 = 𝑬𝝍 (Compact form: 𝑯 - Hamiltonian)
 Example Wavefunctions
• The wave function for a freely moving particle is
sinx or sinkx. (de Broglie’s matter wave).

• The wavefunction of a particle free to oscillate to-

;𝑥 2
and-fro near a point is proportional to 𝑒 . (where
x is the displacement)

• The wavefunction for an electron in the lowest

energy state of a hydrogen atom is proportional to
𝑒 ;𝑟 . (where r is the distance from the nucleus)
 An example Wavefunction

2𝜋𝑥
• 𝜓 𝑥 = sin
𝜆
 The solution of the Schrödinger
2
Equation for a Free Particle
ℏ 𝑑2 𝜓
• − = 𝐸𝜓 V(x) = 0
2𝑚 𝑑𝑥 2

• Let Ψ(x) = sinkx be the solution

(2𝑚𝐸)1/2
• 𝑘=
ℏ
𝑝2
• 𝐸 = 𝐸𝑘 =
2𝑚
2𝜋 𝑕 𝑕
• 𝑝 = 𝑘ℏ = × =
𝜆 2𝜋 𝜆
• In case of free particle:
Schrödinger eqn. leads to de Broglie relation which is
experimentally verified.
 The Born Interpretation
• The probability of finding the particle in a
small region of space of volume δV is
proportional to Ψ2δV where Ψ is the wave
function. (δV – in small volume, Ψ may
be assumed to be constant)
• Whenever Ψ2 is large, there is a high
probability of finding the particle.
• Whenever Ψ2 is small, there is only a
small probability of finding the particle.
 Interpreting a Wavefunction
• a) Ψ b) Ψ2 c) Probability density
 Interpreting a Wavefunction
• Wavefunction must be
 single-valued, not infinite over a finite region
 continuous, having a continuous slope (provided
no abrupt potential energy change) within the
boundary or space considered, finite value upon
square integration.
1s orbital
Hydrogen
atom
Wavefunction
 Interpreting a Wavefunction
• Example Problem : Is this wavefunction
acceptable? Why?
 Interpreting a wavefunction
• Example Problem: The wavefunction of an
electron in the lowest energy state of a hydrogen
−𝑟
atom is proportional to 𝑒 (𝑎𝑜 = 52.9 pm).
𝑎𝑜

Calculate the ratio of probabilities of finding the

electron in a small cubic volume (1 pm3) located
at the nucleus and at a distance r = 𝑎𝑜 . [Ans:
7.4]
Interpreting a wavefunction: Example
Problem
• Given: 𝛿𝑉 = 1 𝑝𝑚3 as region of interest
−𝑟
following 𝑒 𝑎𝑜 as a function of r from the
−2×0
nucleus. At nucleus: Probability ∝ 𝑒 𝑎𝑜 ×1
𝑝𝑚3 ----(A)
−2×𝑎𝑜
At a distance 𝑟 = 𝑎𝑜 : Probability ∝ 𝑒 𝑎𝑜 ×1
𝑝𝑚3 -------(B)
1
Ratio of probabilities: (A) / (B) =
0.14
~7.4
Note: An illustration for this problem is in the new edition of the prescribed text book.
 Acceptable solutions to Schrödinger
Equation
• The fact: only some solutions are acceptable
• Each solution corresponds to a characteristic value
of Energy.
• When the Schrödinger eqn. is solved subject to the
boundary conditions that the solutions must satisfy,
it is found that the energy of the system is quantized.
 Kinetic Energy of Particle
ℏ 2 𝑑2𝜓
• − refers to kinetic energy term of a
2𝑚 𝑑𝑥 2
particle in Schrödinger equation
 The Uncertainty Principle
• Heisenberg’s Uncertainty Principle:
It is impossible to specify simultaneously, with
arbitrary precision, both the momentum and position of
a particle.
 Superposition of Wavefunctions
• Larger number of waves on superposition
gives better accuracy for the position.
The uncertainty Principle: Illustration

• Example Problem: Identify in which case

(a) or (b) position of the particle is certain.

ℏ
∆𝒑𝒙 ∆𝒙 ≥
𝟐
Heisenberg’s
uncertainty
relation
 The uncertainty principle: Example

• Example Problem: Estimate the minimum

uncertainty in the speed of an electron in a
hydrogen atom within its diameter of 100
pm.
ℏ
Eqns. To use: ∆𝒑𝒙 ∆𝒙 ≥
𝟐
ℏ = 1.054 × 10-34 Js
ℏ
m×∆v×∆x ≥ ; given ∆x = 100 pm,
𝟐
m: mass of electron = 9.109 × 10-31 kg
ℏ
𝑴𝒊𝒏𝒊𝒎𝒖𝒎 𝒖𝒏𝒄𝒆𝒓𝒕𝒂𝒊𝒏𝒕𝒚 𝒊𝒏 𝒔𝒑𝒆𝒆𝒅 ∆v = =?
𝟐𝒎∆𝒙
 7C: Translation
• Motion in one dimension:
Schrödinger equation:
2 2
ℏ 𝑑 𝜓
− 2
+ 𝑉 𝑥 𝜓 = 𝐸𝜓
2𝑚 𝑑𝑥
 Particle of mass m is
confined between two
walls.

 The box dimension is L

 The potential energy, V =

0 inside and rises to
infinity at the walls.
 Solution to Particle-in-1d-box
ℏ 2 𝑑2𝜓
• − = 𝐸𝜓 (V = 0 inside the box)
2𝑚 𝑑𝑥 2
• The solution for particle-in-1d-box is:
𝑛𝜋𝑥
𝜓𝑛 (𝑥) = 𝑁𝑠𝑖𝑛
𝐿
[For particle-in-1d-box: Applying boundary
condition]
 Wavelength and kinetic energy:
𝑕 𝑕 𝑝2
𝜆= = and 𝐸𝑘 =
𝑝 (2𝑚𝐸)1/2 2𝑚
(de Broglie’s matter wave and kinetic energy of
confined particle)
 Solution to Particle-in-1d-box
• Applying boundary condition:
𝑛𝜋𝑥
 𝜓𝑛 (𝑥) = 𝑁𝑠𝑖𝑛 = 0 # At x = 0 and x = L
𝐿
The solution for Particle-in-1d-box:
𝑛𝜋𝑥
𝜓𝑛 (𝑥) = 𝑁𝑠𝑖𝑛 with n = 1, 2….
𝐿
2𝜋𝐿 2𝐿 2𝐿 𝒑𝟐 𝒏𝟐 𝒉𝟐
 = 𝑛𝜋 or = 𝑛, 𝜆 = ,𝑬𝒏 = =
𝜆 𝜆 𝑛 𝟐𝒎 𝟖𝒎𝑳𝟐
(Only kinetic energy)
Example Problem: Why is it that n = 0 not
considered in particle-in-1d box?
Allowed Energy Levels for Particle-in-
1d-box
𝟐 𝟐𝑳
𝝀= 𝟐𝑳, 𝑳, 𝑳, . . 𝒐𝒓 𝝀= for n = 1, 2, 3…
𝟑 𝒏

𝒏𝟐 𝒉𝟐
𝑬𝒏 =
𝟖𝒎𝑳𝟐
 Normalization Constant
𝐿 2
• 0
𝜓 𝑑𝑥 =1
2
2 𝐿 𝑛𝜋𝑥
• 𝑁 0 𝑠𝑖𝑛 𝑑𝑥 = 1
𝐿
Using standard integral:
𝑥 𝑠𝑖𝑛2𝑎𝑥
𝑠𝑖𝑛2 𝑎𝑥 𝑑𝑥 = − + 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
2 4𝑎
2
𝐿 𝑛𝜋𝑥
where 0
𝑠𝑖𝑛 𝑑𝑥 = (1/2) × 𝐿
𝐿

2
• 𝑁= NORMALIZATION CONSTANT
𝐿
 Energies of a particle in 1-d-box
• Energies of particle-in-1d-box:

𝒏𝟐 𝒉 𝟐
𝑬𝒏 =
𝟖𝒎𝑳𝟐
• Example Problems:
 What will be the difference in energy between
two adjacent energy levels?
 What is zero point energy?
 What is probability density in terms of x?
 Particle in 1-d-box: Some important
points
 Energy difference between levels:
2 2
ℎ ℎ
∆𝐸 = 𝐸𝑛:1 − 𝐸𝑛 = 𝑛 + 1 2 − 𝑛 2
8𝑚𝐿2 8𝑚𝐿2
𝑕2
= (2𝑛 + 1)
8𝑚𝐿2
 Zero-point energy (ZPE):
𝑕2
𝐸𝑍𝑃𝐸 =
8𝑚𝐿2
 Probability density in terms of x:
2
2 2
𝑛𝜋𝑥
𝜓𝑛 𝑥 = 𝑠𝑖𝑛
𝐿 𝐿
 Discrete Energy Levels: factors
affecting energy separation
• Example Problem: What is the effect of
box dimension and mass of particle on
energy levels?
NARROW BOX WIDE BOX
 Discrete Energy Levels: factors affecting
energy separation and probability density
• The greater the extent of confining region, the
less important the effects of quantization.

• The greater the mass of the particle, the less

effect the effects of quantization.

• For very large value of n (e.g., n = 50),

probability density curve has closely spaced
maxima and nodes.
 Particle-in-1d-box Approximation to
Chemical Systems
• β-carotene: is a linear polyene in which 10 single
and 11 double bonds alternate along a chain of
22 carbon atoms (22π electrons).
• Ground state to the next higher excited state:
𝜟𝑬 = 𝑬𝟏𝟐 − 𝑬𝟏𝟏
 Particle-in-1d-box Approximation to
Chemical Systems: β-carotene
n = 12 (LUMO)
ΔE n = 11 (HOMO)

π-electron
 Each C-C bond
length = 140 pm Filling in β-carotene

 Size of the box:

140 pm
× 21 = 2.94 nm. (𝟐𝒏 + 𝟏)𝒉𝟐
𝜟𝑬 =
𝟖𝒎𝒆 𝑳𝟐
 Transition from
ground state to
the next excited
state: n = 11 to
n = 12
Electron
 Quantum mechanical tunneling:
Qualitative explanation
• If the potential energy, V, of the particle does not
rise to infinity but to some finite value at the wall,
the wavefunction does not abruptly decay to
zero.
• Decays exponentially at the walls and oscillates
on the other side of the wall.
 Quantum mechanical tunneling: An
example from chemical systems
• The rapid proton transfer reactions at very low
temperatures are examples of proton tunneling
when other reactant species cannot overcome
activation barrier.
 Quantum confinement in two
dimensions (2d box): Separation of
variables
 Total Energy in 2d box as per Schrödinger
equation:
𝐻𝑥 𝜓 + 𝐻𝑦 𝜓 = 𝐸𝜓
 The energy operator acts independently along x
and y.
 Quantum confinement in two
dimensions (2d box): Separation of
variables
ℏ2 𝜕2 𝜓 ℏ2 𝜕2 𝜓
•− 2 − 2 = 𝐸𝜓
2𝑚 𝜕𝑥 2𝑚 𝜕𝑦
• Step 1: Express the overall wavefunction as
product of two wavefunctions.
• 𝜓(𝑥, 𝑦) = 𝑋𝑌 where X = X(x) and Y = Y(y)
are wave functions along x-direction and y-
direction, respectively. 𝐻𝑥 only for X and
𝐻𝑦 only for Y
• 𝑌𝐻𝑥 𝑋 + 𝑋𝐻𝑦 𝑌 = 𝐸 × 𝑋𝑌--------(C)
 Quantum confinement in two
dimensions (2d box): Separation of
variables
• Step 2: Divide both sides of (C) by XY
1 1
• 𝐻𝑥 𝑋 + 𝐻𝑦 𝑌 = 𝐸 where
𝑋 𝑌
1 1
𝐻𝑥 𝑋 = 𝐸𝑥 or 𝐻𝑥 𝑋 = 𝐸𝑥 𝑋 and 𝐻𝑦 𝑌 = 𝐸𝑦
𝑋 𝑌
or 𝐻𝑦 𝑌 = 𝐸𝑦 𝑌
 Total Energy: 𝑬𝒙 +𝑬𝒚 = 𝑬
• Step 3: Write the solutions for the energy levels
in 2d box
 Quantum confinement in two
dimensions (2d box): Wavefunction
• According to Separation of variables
procedure:
𝜓 𝑥, 𝑦 = 𝑋 𝑥 𝑌 𝑦
𝜓𝑛𝑥 𝑛𝑦 𝑥, 𝑦 = 𝑋𝑛𝑥 (𝑥) 𝑋𝑛𝑦 (𝑦)
1 2 1 2
2 𝑛𝑥 𝜋𝑥 2 𝑛𝑦 𝜋𝑦
= 𝑠𝑖𝑛 𝑠𝑖𝑛
𝐿𝑥 𝐿𝑥 𝐿𝑦 𝐿𝑦
1 2
4 𝑛𝑥 𝜋𝑥 𝑛𝑦 𝜋𝑦
= 𝑠𝑖𝑛 𝑠𝑖𝑛
𝐿𝑥 𝐿𝑦 𝐿𝑥 𝐿𝑦
𝑛𝑥 , 𝑛𝑦 = 1, 2,……
 Quantum confinement in two
dimensions (2d box): Energy equation
2 𝑕2 2 𝑕2
𝑛𝑦
𝑛𝑥
• 𝐸𝑛𝑥, 𝑛𝑦 = 𝐸𝑛𝑥 + 𝐸𝑛𝑦 = +
8𝑚𝐿2𝑥 8𝑚𝐿2𝑦
2 2
𝑛𝑥 𝑛𝑦 𝑕2
• 𝐸𝑛𝑥, 𝑛𝑦 = [ 2 + 2 ]
𝐿𝑥 𝐿𝑦 8𝑚
 Quantum confinement in two
dimensions (2d box): Wavefunctions
• First three wavefunctions of a particle
confined to a rectangular surface:
 Quantum confinement in two
dimensions (2d box): Example
• Calculate the zero-point energy of an
electron trapped in a 2d box of dimensions
Lx = 1 nm and Ly = 2 nm.
𝐸1,1 =
−34 2
12 12 6.626×10 𝐽𝑠
+ ×
1×10−9 𝑚 2 2×10−9 𝑚 2 8×(9.109×10−31 𝑘𝑔)
=?
 Quantum confinement in 2d box:
Square box and degeneracy
• 2d-Square Box: Lx = Ly = L
 Quantum confinement in 2d box:
Square box and degeneracy
2 𝜋𝑥 2𝜋𝑦
• 𝜓1,2 𝑥, 𝑦 = 𝑠𝑖𝑛 𝑠𝑖𝑛
𝐿 𝐿 𝐿
2 2𝜋𝑥 𝜋𝑦
• 𝜓2,1 𝑥, 𝑦 = 𝑠𝑖𝑛 𝑠𝑖𝑛
𝐿 𝐿 𝐿
The wavefunctions are different, but
energy is same.
5𝑕2
𝐸1,2 = 𝐸2,1 =
8𝑚𝐿2
Different wavefunctions of same energy
are said to be degenerate
 Quantum confinement in 2d box:
Square box and degeneracy
• For a particle in a square box rotation through
90o changes the wavefunction, but the energy
remains same:
DEGENERATE ENERGY LEVELS

𝑛𝑥 = 1, 𝑛𝑦 = 2 𝑛𝑥 = 2, 𝑛𝑦 = 1

Energy 𝑛𝑥 = 1, 𝑛𝑦 = 1
Note: An illustration for this degeneracy is available
in the new edition of the prescribed text book.
7E Vibration: The harmonic oscillator

𝑹𝒆𝒔𝒕𝒐𝒓𝒊𝒏𝒈 𝒇𝒐𝒓𝒄𝒆 =
− 𝒌𝒙 : Hook’s Law
Potential energy:
𝟏
𝑽 𝒙 = 𝒌𝒙𝟐
𝟐
 Potential energy of a Harmonic
oscillator
𝑑𝑉
𝐹=−
𝑑𝑥
𝑑𝑉 = −𝐹𝑑𝑥, 𝐹 𝑥 = −𝑘𝑓 𝑥
𝑥 𝑥
𝑉 𝑥 −𝑉 0 =− 𝐹 𝑥 𝑑𝑥 = − (−𝑘𝑓 𝑥)𝑑𝑥
0 0
𝑉 0 = 0 𝑎𝑡 𝑥 = 0
1
𝑉 𝑥 = 𝑘𝑓 𝑥 2
2
 Vibration: The quantum mechanical
treatment
ℏ2 𝑑 2 𝜓 1
• − + 𝑘𝑓 𝑥 2 𝜓
= 𝐸𝜓
2𝑚 𝑑𝑥 2 2
 Schrödinger eqn. has nonzero potential energy.
 Must satisfy boundary condition
(−∞ 𝑡𝑜 + ∞) as Ψ goes to zero at these
extremities
1
 Solution: 𝐸𝑣 = v + ℎν v = 0,1,2 … (quantum
2
no.)
1 𝑘𝑓
ν = | Quantized energies of the harmonic
2𝜋 𝜇
𝑚𝐴 𝑚𝐵
oscillator where 𝜇 =
𝑚𝐴 :𝑚𝐵
 Vibrational energy levels
1
• 𝐸𝑍𝑃𝐸,𝑣𝑖𝑏 = ℎ𝜈 and Δ𝐸 = ℎ𝜈
2
 Vibrational frequency of a chemical
bond
• Example Problem: The force constant for
an H-Cl bond is 516 N m-1. Assuming Cl is
heavy compared to H, calculate the
frequency of vibration of this chemical
bond. (mH = 1.67 × 10-27 kg)
1 𝑘𝑓
𝜈 = =? H Cl
2𝜋 𝑚𝐻

∆𝐸 = ℎ𝜈 =?
 Vibrational energy levels:
Normalization of ground state
•
wavefunction
For vibrational quantum number: v = 0
𝑎𝑥2
;
𝜓(𝑥) = 𝑁𝑒 2

(Format of eqn. as per the problem 12.36 in 6th edn.)

 The wavefunctions are expressed in terms of the
variable x.
 Through a normalization step and using standard
:∞ ;𝑎𝑥 2 𝜋 1 2
integral: ;∞
𝑒 𝑑𝑥 =
𝑎
2 :∞ ;𝑎𝑥 2
 𝑁 ;∞ 𝑒 𝑑𝑥 = 1
𝑎 1 4
 𝑁= where 𝑎 is a parameter that depends on force
𝜋
constant and (reduced) mass of the given system.
Vibrational energy levels:
Wavefunctions
 Vibrational energy levels:
Wavefunctions
• The lowest energy wavefunction (v = 0) is a bell-
;𝑥 2
shaped curve of the form 𝑒 with no nodes
• The first excited wavefunction (v = 1) has a node
at x = 0 with positive and negative peaks on
either side.
• All the wavefunctions extend beyond the limits of
classical oscillator.
• At high value of quantum number (e.g., v = 25),
the probability density is maximum at
extremities.
 First four Vibrational energy levels:
Sketches of Wavefunction and
Probability density
• Wave function Probability density

v=4
v=4
v=3
v=3
v=2
v=2
v=1
v=1

v=0
v=0
Vibrational energy levels: Probability
density
Summary of Equations

Particle in 2-d box

2 2
𝑛𝑥 𝑛𝑦 𝑕2
𝐸𝑛𝑥, 𝑛𝑦 = [ 𝐿2 + 𝐿2 ] 8𝑚
𝑥 𝑦
 Additional resources
• https://www.bloomberg.com/features/2019-periodic-table-elements-
issue/?utm_source=Nature%20Briefing&utm_campaign=6a5603f838-
briefing-dy-20190829&utm_medium=email&utm_term=0_c9dfd39373-
6a5603f838-42935443#cobalt-nickel-copper-zinc
( Periodic Table @150th year)
• http://www.rsc.org/learn-chemistry/collections/spectroscopy
(Basic concepts of spectrosopy)