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Focus 7: Quantum Theory: Elements of Physical Chemistry, Peter Atkins and Julio de Paula, International Edition
Focus 7: Quantum Theory: Elements of Physical Chemistry, Peter Atkins and Julio de Paula, International Edition
c = νλ
The Electromagnetic Spectrum:
400 nm- 800 nm
The Electromagnetic Spectrum:
Color Wheel
∆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
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).
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
ℏ
∆𝒑𝒙 ∆𝒙 ≥
𝟐
Heisenberg’s
uncertainty
relation
The uncertainty principle: Example
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.
π-electron
Each C-C bond
length = 140 pm Filling in β-carotene
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
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