CY3206

Quantum Chemistry
and its Applications

Dr. Susruta Samanta

Department of Chemistry
(susruta.samanta@jaipur.manipal.edu)
Dr. Susruta Samanta
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Max Planck Erwin Schrödinger Luis de Broglie

Heisenberg Albert Einstein

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The Wave Equation
(1925) Erwin Schrödinger and Werner Heisenberg independently formulated a general quantum theory.
• Heisenberg's method is formulated in terms of matrices.
• Schrödinger's method is formulated in terms of partial differential equations.
• Schrödinger showed that the two formulations are mathematically equivalent.

(for most of the chemists, partial differential equations are easier than matrices)
(may not sound very comforting, but we need only elementary calculus)

Schrödinger equation

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The Schrödinger Wave Equation
• We know that matter can behave as a wave
• Schrödinger’s wave equation describes wavelike behaviour of matter
• Schrödinger showed that the two formulations are mathematically equivalent
• The wave equation of classical physics describes various wave phenomena
vibrating string, a vibrating drumhead, ocean waves, and acoustic waves
• The classical wave equation provide a physical background to the Schrödinger equation
• The mathematics involved in solving the classical wave equation are central to any discussion of
quantum mechanics.

We will solve the standard problem of a vibrating string because not only is the method of solving this
problem like the method we will use to solve the Schrödinger equation

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The Wave Equation:
A vibrating string

• Amplitude → maximum displacement of the string from its equilibrium horizontal position
𝛿 2𝑢 1 𝛿 2𝑢
2
= 2 2
𝛿𝑥 𝑣 𝛿𝑡
This equation is a linear partial differential equation, and it is the classical wave equation
• 𝑥 and 𝑡 are independent variables
• 𝑢 𝑥, 𝑡 = 𝑓 𝑥, 𝑡 → dependent variable
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The Wave Equation:
A vibrating string

Conditions →
• Ends are fixed, displacements at the ends are zero. Hence, for any 𝑡,
𝑢 0, 𝑡 = 0 & 𝑢 𝑙, 𝑡 = 0

• These are the boundary conditions

• Partial differential equations need boundary conditions to solve them

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The Wave Equation:
A vibrating string
Solution →
𝑑2 𝑢 1 𝑑2 𝑢
2
= 2 2
𝑑𝑥 𝑣 𝑑𝑡
• We apply a method called separation of variables
𝑢 𝑥, 𝑡 = 𝑋 𝑥 . 𝑇 𝑡
𝑑2 𝑋 𝑥 1 𝑑 2 𝑇(𝑡)
𝑇(𝑡) 2
= 2 𝑋(𝑥)
𝑑𝑥 𝑣 𝑑𝑡 2
• Divide both sides by 𝑋 𝑡 . 𝑇 𝑡
1 𝑑2 𝑋 𝑥 1 𝑑 2 𝑇(𝑡)
2
= 2
𝑋 𝑥 𝑑𝑥 𝑣 𝑇(𝑡) 𝑑𝑡 2
• The LHS is 𝑓 𝑥 and RHS is 𝑓(𝑡) only and they are independent variables, can be solved separately

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The Wave Equation:
A vibrating string
Solution →
1 𝑑2 𝑋 𝑥 1 𝑑 2 𝑇(𝑡)
2
= 2 2
=𝐾
𝑋 𝑥 𝑑𝑥 𝑣 𝑇(𝑡) 𝑑𝑡
• 𝐾 is the separation constant → later!
• Now,

𝑑2 𝑋 𝑥 𝑑 2 𝑇(𝑡)
− 𝐾𝑋 𝑥 = 0 & − 𝐾𝑣 2𝑇 𝑡 = 0
𝑑𝑥 2 𝑑𝑡 2

• These are ordinary differential equations → linear differential equations with constant coefficients
• Easy to solve

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The Wave Equation:
A vibrating string
Value of K?
• 𝐾 can be positive, negative, zero
• Let’s assume 𝐾 = 0

𝑑2 𝑋 𝑥 𝑑 2 𝑇(𝑡) 2𝑇 𝑡 = 0
2
− 𝐾𝑋 𝑥 = 0 − 𝐾𝑣
𝑑𝑥 𝑑𝑡 2
𝑋 𝑥 = 𝑎1 𝑥 + 𝑏1 𝑇 𝑡 = 𝑎2 𝑡 + 𝑏2

𝑎, 𝑏 are integration constants and can be solved using boundary conditions

• 𝑢 0, 𝑡 = 𝑋 0 𝑇 𝑡 = 0
• 𝑢 𝑙, 𝑡 = 𝑋 𝑙 𝑇 𝑡 = 0
• 𝑇 𝑡 ≠ 0 as it does not vanish for all 𝑡, hence, 𝑋 0 = 0 and 𝑋 𝑙 = 0
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The Wave Equation:
A vibrating string
Value of K?
• 𝐾 can be positive, negative, zero
• Let’s assume 𝐾 = 0

𝑑2 𝑋 𝑥 𝑑 2 𝑇(𝑡) 2𝑇 𝑡 = 0
2
− 𝐾𝑋 𝑥 = 0 − 𝐾𝑣
𝑑𝑥 𝑑𝑡 2
𝑋 𝑥 = 𝑎1 𝑥 + 𝑏1 𝑇 𝑡 = 𝑎2 𝑡 + 𝑏2

• 𝑇 𝑡 ≠ 0 as it does not vanish for all 𝑡, hence, 𝑋 0 = 0 and 𝑋 𝑙 = 0

• Hence, a1 = b1 = 0
• 𝑋 𝑥 = 0 and 𝑢 𝑥, 𝑡 = 0 for all 𝑥
• This is the trivial solution, and it is pointless to us (of no interest)
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The Wave Equation:
A vibrating string
Value of K?
• Let’s assume 𝐾 > 0 (we write 𝐾 = 𝑘 2 )
𝑑2 𝑋 𝑥 2𝑋 𝑥 = 0
− 𝑘
𝑑𝑥 2

• These have solution in the form 𝑋 𝑥 = 𝑒 𝛼 𝑥 [the constant 𝛼 needs to be determined]

𝑋 𝑥 = 𝑒𝛼𝑥
𝛼 2 − 𝑘 2 . 𝑋(𝑥) = 0
• Therefore, 𝛼 2 − 𝑘 2 = 0 or 𝑋(𝑥) = 0
• 𝑋 𝑥 = 0 is the trivial solution and hence 𝛼 2 − 𝑘 2 = 0
𝛼 = ±𝑘

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The Wave Equation:
A vibrating string
Value of K?
• Let’s assume 𝐾 > 0
• There are two solutions:
𝑋 𝑥 = 𝑒 𝑘𝑥 𝑜𝑟 𝑒 −𝑘𝑥
𝑋 𝑥 = 𝑐1 𝑒 𝑘𝑥 + 𝑐2 𝑒 −𝑘𝑥
• This is the second solution.
• Applying the boundary conditions:
𝑐1 + 𝑐2 = 0 and 𝑋 𝑥 = 𝑐1 𝑒 𝑘𝑙 + 𝑐2 𝑒 −𝑘𝑙 = 0
• Again, this means 𝑐1 = 𝑐2 = 0 → trivial solution
• If 𝐾 = 0 or 𝐾 > 0, we find only the trivial solution

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The Wave Equation:
A vibrating string
Value of K?
• Let’s assume 𝐾 < 0 (Let’s hope to get an interesting solution) (we write 𝐾 = −𝛽2 )
𝛿 2𝑋 𝑥 2𝑋 𝑥 = 0
+ 𝛽
𝛿𝑥 2
𝑋 𝑥 = 𝑒 𝛼𝑥 → 𝛼 2 + 𝛽2 . 𝑋 𝑥 = 0
𝛼 = ±𝑖𝛽

The general solution of this is:

𝑿 𝒙 = 𝑨 𝒄𝒐𝒔 𝜷𝒙 + 𝑩 𝒔𝒊𝒏 𝜷𝒙
The boundary conditions that 𝑋 0 = 0 implies that 𝐴 = 0 &
𝑋 𝑙 = 𝐵 sin 𝛽𝑙 = 0

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The Wave Equation:
A vibrating string
Value of K?
• Let’s assume 𝐾 < 0 (Let’s hope to get an interesting solution) (we write 𝐾 = −𝛽2 )
𝛿 2𝑋 𝑥 2𝑋 𝑥 = 0
+ 𝛽
𝛿𝑥 2
𝑋 𝑥 = 𝑒 𝛼𝑥 → 𝛼 2 + 𝛽2 . 𝑋 𝑥 = 0
𝛼 = ±𝑖𝛽
𝑿 𝒙 = 𝒄𝟏 𝒆𝒊𝜷𝒙 + 𝒄𝟐 𝒆−𝒊𝜷𝒙
𝑒 ±𝑖𝜃 = 𝑐𝑜𝑠𝜃 ± 𝑖 𝑠𝑖𝑛𝜃
Using Euler’s formula
𝑋 𝑥 = 𝑐1 cos 𝛽𝑥 + 𝑖 sin 𝛽𝑥 = 𝑐2 cos 𝛽𝑥 − 𝑖 sin 𝛽𝑥
= (𝑐1 +𝑐2 ) cos 𝛽𝑥 + (𝑖𝑐1 − 𝑖𝑐2 ) sin 𝛽𝑥
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The Wave Equation:
A vibrating string
Value of K?
• Let’s assume 𝐾 < 0 (Let’s hope to get an interesting solution)
𝑋 𝑥 = (𝑐1 +𝑐2 ) cos 𝛽𝑥 + (𝑖𝑐1 − 𝑖𝑐2 ) sin 𝛽𝑥
• (𝑐1 +𝑐2 ) and (𝑖𝑐1 − 𝑖𝑐2 ) are constants → 𝑐3 & 𝑐4
𝑋 𝑥 = 𝑐3 cos 𝛽𝑥 + 𝑐4 sin 𝛽𝑥

The general solution of this is:

𝑿 𝒙 = 𝑨 𝒄𝒐𝒔 𝜷𝒙 + 𝑩 𝒔𝒊𝒏 𝜷𝒙
The boundary conditions that 𝑋 0 = 0 implies that 𝐴 = 0 &
𝑋 𝑙 = 𝐵 sin 𝛽𝑙 = 0

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The Wave Equation:
A vibrating string
Value of K?
The general solution of this is: 𝑿 𝒙 = 𝑨 𝒄𝒐𝒔 𝜷𝒙 + 𝑩 𝒔𝒊𝒏 𝜷𝒙
𝑋 𝑙 = 𝐵 sin 𝛽𝑙 = 0
Two solutions:
• 𝐵 = 0 → trivial solution
• sin 𝛽𝑙 = 0 → sin 𝜃 = 0 𝑎𝑡 𝜃 = 𝜋, 2𝜋, 3𝜋 …
Hence, 𝛽𝑙 = 𝑛𝜋, 𝑛 = 1,2,3 …
(we don’t consider 𝑛 = 0, as that would point to the trivial solution)
𝒏𝝅𝒙
𝑿 𝒙 = 𝑩 𝐬𝐢𝐧
𝒍

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The Schrӧdinger’s Wave Equation:
Electrons are considered as standing waves with an amplitude 𝝍
𝒙
𝝍 = 𝑨 𝒔𝒊𝒏 𝟐𝝅
𝝀
Let’s solve the differential equation for this:
𝑑𝜓 2𝜋 𝑥
=𝐴 𝑐𝑜𝑠 2𝜋
𝑑𝑥 𝜆 𝜆
𝑑2 𝜓 4𝜋 2 𝑥
= −𝐴 2 𝑠𝑖𝑛 2𝜋
𝑑𝑥 2 𝜆 𝜆
𝑥
But A 𝑠𝑖𝑛 2𝜋 = 𝜓, and hence
𝜆

𝑑2 𝜓 4𝜋 2
=− 2 𝜓
𝑑𝑥 2 𝜆

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The Schrӧdinger’s Wave Equation:
Electrons are considered as standing waves with an amplitude 𝝍
Kinetic energy (KE) of a particle:
1 2
1 𝑚2 𝑣 2
𝐾𝐸 = 𝑚𝑣 =
2 2 𝑚
According to de Broglie hypothesis
ℎ
𝜆=
𝑚𝑣
ℎ 2 ℎ 2
𝜆2 = 2 2 → 𝑚2 𝑣 2 = 2
𝑚 𝑣 𝜆
So, KE becomes
1 1 𝑚 2𝑣 2 1 ℎ 2
𝐾𝐸 = 𝑚𝑣 2 = =
2 2 𝑚 2 𝑚𝜆2

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The Schrӧdinger’s Wave Equation:
Electrons are considered as standing waves with an amplitude 𝝍
We know:
𝑑2 𝜓 4𝜋 2
2
=− 2 𝜓
𝑑𝑥 𝜆
4𝜋 2 𝜓
𝜆2 =− 2
𝑑 𝜓
𝑑𝑥 2
So, KE becomes
1 1 𝑚 2𝑣 2 1 ℎ 2
𝐾𝐸 = 𝑚𝑣 2 = =
2 2 𝑚 2 𝑚𝜆2

𝟏 𝒉𝟐 𝒅𝟐 𝝍 𝒉𝟐 𝒅𝟐 𝝍
𝑲𝑬 = − 𝟐 𝟐
=− 𝟐
𝟐𝒎 𝟒𝝅 𝝍 𝒅𝒙 𝟖𝝅 𝒎𝝍 𝒅𝒙𝟐
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The Schrӧdinger’s Wave Equation:
𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 = 𝐾. 𝐸. +𝑃. 𝐸.
ℎ2 𝑑 2 𝜓
𝐾. 𝐸. = 𝑇𝑜𝑡𝑎𝑙 𝑒𝑛𝑒𝑟𝑔𝑦 − 𝑃. 𝐸. = − 2
8𝜋 𝑚𝜓 𝑑𝑥 2
𝒅𝟐 𝝍 𝟖𝝅𝟐 𝒎
𝟐
=− 𝟐
𝑬 − 𝑷𝑬 𝝍
𝒅𝒙 𝒉

𝒅𝟐 𝝍 𝒅𝟐 𝝍 𝒅𝟐 𝝍 𝟖𝝅𝟐 𝒎
+ + + 𝑬 − 𝑷𝑬 𝝍 = 𝟎
𝒅𝒙𝟐 𝒅𝒚𝟐 𝒅𝒛𝟐 𝒉𝟐

𝟐
𝟐
𝟖𝝅 𝒎
𝛁 𝝍+ 𝑬 − 𝑷𝑬 𝝍 = 𝟎
𝒉𝟐

𝑑2 𝑑2 𝑑2
𝛻2 = + + is known as the Laplacian operator
𝑑𝑥 2 𝑑𝑦 2 𝑑𝑧 2

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The Schrӧdinger’s Wave Equation:
𝑑2 𝜓 8𝜋 2 𝑚
2
=− 2 𝐸 − 𝑃𝐸 𝜓
𝑑𝑥 ℎ
Properties
• Schrödinger’s wave equation is a second-degree differential equation
• It has several solutions – some of them imaginary/not valid
• If we know 𝑃𝐸, the total energy 𝐸 and the corresponding wave function 𝜓 can be evaluated
• The wave function is always finite, single valued and continuous
• It is zero at infinite distance
• Solutions that meet these requirements are only possible if E is given certain characteristic values
• These characteristic values of wavefunction ψ and are called Eigen values
• The Bohr’s model may be considered as a direct consequence of wave mechanical approach

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CY3206

Quantum Chemistry
and its Applications

Dr. Susruta Samanta

Department of Chemistry
(susruta.samanta@jaipur.manipal.edu)

Dr. Susruta Samanta

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Dr. Susruta Samanta
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The Schrӧdinger’s Wave Equation:
𝑑2 𝜓 8𝜋 2 𝑚
2
=− 2 𝐸 − 𝑃𝐸 𝜓
𝑑𝑥 ℎ

𝑑 2 𝜓 𝑑 2 𝜓 𝑑 2 𝜓 8𝜋 2 𝑚
+ + + 𝐸 − 𝑃𝐸 𝜓 = 0
𝑑𝑥 2 𝑑𝑦 2 𝑑𝑧 2 ℎ2

Physical significance of 𝜓:
• 𝜓 is the quantum analogous to amplitude of a stationary wave
• 𝜓 is not a physically observable quantity
• 𝜓 can be used to determine other properties of a system
• 𝜓 is called the wave function

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The Schrӧdinger’s Wave Equation:
𝑑2 𝜓 8𝜋 2 𝑚
2
=− 2 𝐸 − 𝑃𝐸 𝜓
𝑑𝑥 ℎ

Physical significance of 𝜓 𝟐 :
• 𝜓 2 or 𝜓 𝜓 ∗ is always a real quantity
• If 𝜓 is complex, 𝜓 ∗ is its complex conjugate
If 𝜓 = 𝐴𝑒 𝑖𝑥 , then 𝜓 ∗ = 𝐴∗ 𝑒 −𝑖𝑥
Then 𝜓 𝜓 ∗ = 𝐴𝑒 𝑖𝑥 × 𝐴∗ 𝑒 −𝑖𝑥 = 𝐴 2

• In classical physics, square of an amplitude at a point represents the energy density

• Not acceptable in QM as that would mean a discontinuous function
• 𝜓 is always continuous

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Dr. Susruta Samanta
The Schrӧdinger’s Wave Equation:
𝑑2 𝜓 8𝜋 2 𝑚
2
=− 2 𝐸 − 𝑃𝐸 𝜓
𝑑𝑥 ℎ
Physical significance of 𝜓 𝟐 :
Einstein’s interpretation:
• 𝜓 2 is the “probability density”
• Probability density: Probability per unit space of finding a particle at that point

Max Born’s interpretation:

• 𝜓 2 is the probability of finding a particle within unit distance, if the particle is moving in one direction

Most useful interpretation:

• For an electron wave, 𝜓 2 or 𝜓 𝜓 ∗ is the “electron density” – “electronic charge per unit space”
• Electrons behave as a cloud of negative charge with non-uniform charge distribution

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Dr. Susruta Samanta
The Schrӧdinger’s Wave Equation:
𝑑2 𝜓 8𝜋 2 𝑚
2
=− 2 𝐸 − 𝑃𝐸 𝜓
𝑑𝑥 ℎ
Physical significance of 𝜓 𝟐 :
In mathematical terms:
𝜓 = 𝜓(𝑥)
• 𝜓 2 𝑑𝑥 or 𝜓 𝜓 ∗ 𝑑𝑥 is the probability of finding the particle in distance 𝑥 and 𝑥 + 𝑑𝑥

𝜓 = 𝜓(𝑥, 𝑦, 𝑧)
• 𝜓 2 𝑑𝑥 𝑑𝑦 𝑑𝑧 or 𝜓 𝜓 ∗ 𝑑𝑥 𝑑𝑦 𝑑𝑧 is the probability of finding the particle in the space 𝑥 and 𝑥 + 𝑑𝑥, 𝑦 and
𝑦 + 𝑑𝑦, 𝑧 and 𝑧 + 𝑑𝑧

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Dr. Susruta Samanta
The Schrӧdinger’s Wave Equation:
𝑑2 𝜓 8𝜋 2 𝑚
2
=− 2 𝐸 − 𝑃𝐸 𝜓
𝑑𝑥 ℎ
Physical significance of 𝜓 𝟐 :
If a system has n number of particles:
• Each particle will have 3 coordinates (𝑥, 𝑦, 𝑧)

• In total 3n coordinates 𝑥1 , 𝑦1 , 𝑧1 , 𝑥2 , 𝑦2 , 𝑧2 … . . 𝑥𝑛 , 𝑦𝑛 , 𝑧𝑛

• In that case, probability of finding the particle is 𝜓 2 𝑑𝑥1 𝑑𝑦1 𝑑𝑧1 𝑑𝑥2 𝑑𝑦2 𝑑𝑧2 … 𝑑𝑥𝑛 𝑑𝑦𝑛 𝑑𝑧𝑛

• 𝑑𝑥1 𝑑𝑦1 𝑑𝑧1 𝑑𝑥2 𝑑𝑦2 𝑑𝑧2 … 𝑑𝑥𝑛 𝑑𝑦𝑛 𝑑𝑧𝑛 is the “volume element of space”

• Represented as 𝒅𝝉

• Probability of finding a particle is 𝜓 2 𝑑𝜏

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Dr. Susruta Samanta
The Schrӧdinger’s Wave Equation:
𝑑2 𝜓 8𝜋 2 𝑚
2
=− 2 𝐸 − 𝑃𝐸 𝜓
𝑑𝑥 ℎ
Properties
• The wave function 𝜓 is always finite
Infinite value of 𝜓 means infinite probability of finding the particle at a single point
• The wave function 𝜓 is always single valued
Probability at any given point should be unambiguous
• The wave function 𝜓 is always continuous
𝑑𝜓
𝜓 and must be continuous – it must not change abruptly
𝑑𝑥
𝑑𝜓 𝑑2 𝜓
must not have an inflection point – would mean =0
𝑑𝑥 𝑑𝑥 2

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Normalization:
𝜓 2 𝑑𝑥 or 𝜓 𝜓 ∗ 𝑑𝑥 represents probability of finding a particle at any point 𝑥
‫ 𝜓 ׬‬2 𝑑𝑥 = 1 or ‫ = 𝑥𝑑 ∗ 𝜓 𝜓 ׬‬1
𝐿
න 𝜓 𝜓 ∗ 𝑑𝑥 = 1
0
𝐿
‫׬‬0 𝜓 𝜓 ∗ 𝑑𝜏 = 1 [𝑑𝜏 = 𝑑𝑥 𝑑𝑦 𝑑𝑧]

• This condition is called the normalization condition

• Any function that satisfies these conditions are called normalized wave functions

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Dr. Susruta Samanta
Normalization:
𝜓 2 𝑑𝑥 or 𝜓 𝜓 ∗ 𝑑𝑥 represents probability of finding a particle at any point 𝑥
‫ 𝜓 ׬‬2 𝑑𝑥 = 1 or ‫ = 𝑥𝑑 ∗ 𝜓 𝜓 ׬‬1
𝐿
න 𝜓 𝜓 ∗ 𝑑𝑥 = 1
0
𝐿
‫׬‬0 𝜓 𝜓 ∗ 𝑑𝜏 = 1 [𝑑𝜏 = 𝑑𝑥 𝑑𝑦 𝑑𝑧]

• If after solving the Schrodinger wave equation, the wave function does not satisfy the normalization
conditions, we need to use a normalization factor

න 𝜙 2 𝑑𝑥 = 𝑐 ≠ 1

1 1
is the normalization factor, ‫׬‬ 𝜙2 𝑑𝑥 = 1 is the normalized wave function
√𝑐 𝑐

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Dr. Susruta Samanta
Postulates of Quantum Mechanics:
Postulate 1:
• The state of a quantum mechanical system is completely specified by the wavefunction 𝜓(𝑟, 𝑡)
• This function, called the wave function or state function, has the important property that 𝜓 ∗ (𝑟, 𝑡)
𝜓 𝑟, 𝑡 𝑑𝜏 is the probability that the particle lies in the volume element 𝑑𝜏 located at 𝑟 at time 𝑡.
• The wavefunction must satisfy certain mathematical conditions because of this probabilistic
interpretation. For the case of a single particle, the probability of finding it somewhere is 1, so that we
have the normalization condition
∞
න 𝜓 𝑟, 𝑡 𝜓 ∗ 𝑟, 𝑡 𝑑𝜏 = 1
−∞

• It is customary to also normalize many-particle wavefunctions to 1.

• The wavefunction must also be single-valued, continuous, and finite.

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Dr. Susruta Samanta
Postulates of Quantum Mechanics:
Postulate 2:
• To every observable in classical mechanics, there
corresponds a linear, Hermitian operator in
quantum mechanics.

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Dr. Susruta Samanta
Postulates of Quantum Mechanics:
Postulate 3:

• In any measurement of the observable associated with operator 𝐴, መ the only values that will ever be
observed are the eigenvalues 𝑎, which satisfy the eigenvalue equation
መ = 𝑎𝜓
𝐴𝜓
This postulate captures the central point of quantum mechanics – the values of dynamical variables can be
quantized (although it is still possible to have a continuum of eigenvalues in the case of unbound states). If
the system is in an eigenstate of 𝐴መ with eigenvalue 𝑎, then any measurement of the quantity 𝐴መ will yield 𝑎.
Although measurements must always yield an eigenvalue, the state does not have to be an eigenstate of 𝐴መ
initially. An arbitrary state can be expanded in the complete set of eigenvectors of 𝐴መ (𝐴𝜓
መ 𝑖 = 𝑎𝑖 𝜓𝑖 ) as
𝑛

𝜓 = ෍ 𝑐𝑖 𝜓𝑖
𝑖

where 𝑛 may go to infinity.

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Dr. Susruta Samanta
Postulates of Quantum Mechanics:
Postulate 3:

• An arbitrary state can be expanded in the complete set of eigenvectors of 𝐴መ (𝐴𝜓

መ 𝑖 = 𝑎𝑖 𝜓𝑖 ) as
𝑛

𝜓 = ෍ 𝑐𝑖 𝜓𝑖
𝑖

where 𝑛 may go to infinity.

• In this case we only know that the measurement of 𝐴 will yield one of the values 𝑎𝑖 , but we don't know
which one. However, we do know the probability that eigenvalue 𝑎𝑖 will occur – it is the absolute value
squared of the coefficient, 𝑐𝑖 2 , leading to the fourth postulate.
• An important second half of the third postulate is that, after measurement of 𝜓 yields some eigenvalue
𝑎𝑖 , the wavefunction immediately “collapses” into the corresponding eigenstate 𝜓𝑖 (in the case that 𝑎𝑖 is
degenerate, then 𝜓 becomes the projection of 𝜓 onto the degenerate subspace).
• Thus, measurement affects the state of the system. This fact is used in many elaborate experimental
tests of quantum mechanics.
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Dr. Susruta Samanta
Postulates of Quantum Mechanics:
Postulate 4:
• If a system is in a state described by a normalized wave function 𝜓, then the average value of the
observable corresponding to 𝐴መ is given by
∞
< 𝐴 > = න 𝜓 ∗ 𝐴መ 𝜓 𝑑𝜏
−∞

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Dr. Susruta Samanta
Postulates of Quantum Mechanics:
Postulate 5:
• The wavefunction evolves in time according to the time-dependent Schrödinger equation
𝛿𝜓
෡ 𝜓 𝑟, 𝑡 = 𝑖ℏ
𝐻
𝛿𝑡

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Dr. Susruta Samanta
Postulates of Quantum Mechanics:
Postulate 6:
• The total wavefunction must be antisymmetric with respect to the interchange of all coordinates of one
fermion with those of another. Electronic spin must be included in this set of coordinates.
• The Pauli exclusion principle is a direct result of this antisymmetry principle. We will later see that Slater
determinants provide a convenient means of enforcing this property on electronic wavefunctions.

43
Dr. Susruta Samanta
 44
Dr. Susruta Samanta
10 Free particle, particle in a 1D box, Concept of Particle in 1D Box Model Lecture 1514.2
translational energy, energy
levels, quantization of energy,
wave functions for particle in a
box,
11 3D box, Operators, Idea about 3D model and operators Lecture 1514.2
12 Postulates of quantum mechanics Explain Quantum Mechanics and its Lecture 1514.2
Postulates
13 Time dependent Schrödinger Discuss Time dependent Schrödinger Lecture 1514.2 Assignments
equation equation /Class Quiz
14 Expectation values Calculate expectation values of different Lecture 1514.2
MTE-1
operators
15 Applications of particle in a box Understand application of particle one Lecture 1514.2 ETE
model dimensional box in different problems
16 Vibrational motion, classical one- Discuss theory of Vibrational Motion Lecture 1514.2
dimensional harmonic oscillator.,
rotational motion,
17 Quantum mechanical harmonic Getting idea about harmonic oscillator Lecture 1514.2
oscillator
18 Numerical problems NA Interactive/Self study 1514.2
21 Numerical problems NA Interactive/Self study 1514.2

45
Dr. Susruta Samanta
22 Schrödinger equation for Understanding Hydrogen Interactive/ 1514.2
hydrogen-like atoms, elementary atom problem Self study
discussion of its solution
23 Wave functions for hydrogen atom Explain nature of wave Lecture 1514.2
function
24 Electron spin, Concept of spin Getting idea about electron Lecture 1514.2
Assignments/Class Quiz
orbitals spin
MTE-1
25 Spectral selection rules for one- Understanding spectral Lecture 1514.2 ETE
electron atoms, spectrum of selection rule
hydrogen atom
26 Conceptual Problems NA Interactive/ 1514.2
Self study
27 Revision class NA Interactive/ 1514.2
Self study

Dr. Susruta Samanta

Discussions
Questions
Clarifications

47
Dr. Susruta Samanta