Quantum Mechanics

Chapter 1: Wave Nature of Electron & Schrödinger Equation

Complete Exam-Style Answers with Derivations and Diagrams

 Q1. Wave Nature of Electron — Davisson and Germer’s Experiment

Background

In 1924, de Broglie proposed that electrons possess wave nature, expressed by the equation λ = h/mv.
This hypothesis was experimentally confirmed by Davisson and Germer in 1927.

Fig 1.1: Schematic of the

Davisson–Germer electron diffraction experiment

Experimental Setup

A beam of electrons, accelerated through a known potential, was directed at a nickel (Ni) crystal. A
movable detector measured the intensity of scattered electrons at various angles θ.

Observation

At a specific angle (θ = 50◦ ) and accelerating voltage (54 V), a sharp maximum in scattered intensity
was observed. This peak is characteristic of diffraction — a phenomenon unique to waves.

Calculation and Verification

λ (from de Broglie equation) = h/mv = 1.67 Å

λ (from diffraction, Bragg’s law) = 1.65 Å

The two values agree closely, providing direct experimental proof that electrons exhibit wave properties.

Conclusion

The Davisson–Germer experiment experimentally validated de Broglie’s hypothesis and confirmed the
wave-particle duality of matter.

Q2. Application of de Broglie’s Equation to Bohr’s Theory

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Key Idea

If an electron in a Bohr orbit behaves as a standing wave, the circumference of the orbit must contain
a whole number of wavelengths.

Fig 2.1: Standing electron wave fitting around a Bohr

orbit (n = 6)
2πr = nλ . . . (1)

Derivation

Substituting de Broglie’s equation λ = h/mv into equation (1):

2πr = n · (h/mv)

mvr = nh/2π

Important Result

This is exactly Bohr’s quantization condition for angular momentum. This shows that Bohr’s postulate
is not an arbitrary assumption — it emerges naturally from the wave nature of the electron.

Q3. Derivation of Bohr’s Postulate of Quantization of Angular Momentum

Statement

The angular momentum of an electron in any permitted orbit is quantized:

L = mvr = nh/2π

Step-by-step Derivation

Step 1: For a standing wave to exist in a circular orbit without destructive interference, the orbit
circumference must equal a whole number of wavelengths:

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2πr = nλ . . . (1)

Step 2: From de Broglie’s equation:

λ = h/mv . . . (2)

Step 3: Substituting (2) into (1):

2πr = nh/mv

Step 4: Rearranging:
mvr = nh/2π

where n = 1, 2, 3 . . . is the quantum number. This proves that angular momentum is naturally quantized
as a direct consequence of the wave character of the electron.

Q4. The Heisenberg Uncertainty Principle

Statement

It is impossible to simultaneously determine both the exact position and the exact momentum of a
particle with absolute precision.
∆x · ∆p ≥ h/4π

A similar relation holds between energy and time:

∆E · ∆t ≥ h/4π

Symbol Meaning
∆x Uncertainty in position
∆p Uncertainty in momentum
h Planck’s constant

Key point: the more precisely we know the position (∆x small), the less precisely we can know the
momentum (∆p large), and vice versa.

Q5. Physical Concept of Uncertainty Principle (with Problem)

Physical Explanation

To observe an electron, we must illuminate it with photons (e.g., using a hypothetical gamma-ray
microscope). The collision between the photon and electron disturbs the electron’s momentum.

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 Fig 5.1: Trade-off between position certainty and momentum certainty
• Using short-wavelength (high-energy) light gives precise position but causes a large, uncontrollable
disturbance in momentum.
• Using long-wavelength (low-energy) light gives precise momentum but poor position resolution.

Consequences

1. Electrons cannot have well-defined orbits (this contradicts Bohr’s fixed-orbit model).
2. The concept of probability replaces classical certainty.
3. This leads directly to the concept of orbitals (probability regions) instead of orbits.

Example Problem

Q: If the uncertainty in the position of an electron is 10−10 m, find the uncertainty in its velocity.
∆p = h/(4π∆x) = (6.626 × 10−34 )/(4π × 10−10 )

∆p = 5.27 × 10−25 kg·m/s

∆v = ∆p/m = (5.27 × 10−25 )/(9.11 × 10−31 ) = 5.79 × 105 m/s

Q6. Wave Mechanical Concept of Atom

Classical (Bohr) Model Wave Mechanical Model

Electron in a fixed orbit Electron in an orbital (probability region)
Definite, traceable path No definite path
2D circular orbits 3D probability clouds

Key Concepts

1. The electron is treated as a wave, described by a wave function ψ.

2. ψ 2 gives the probability of finding the electron at a given point.
3. An orbital is defined as the region of space where the probability of finding the electron is 90–95%.
4. Energy levels are quantized naturally as a result of solving the wave equation, rather than being
imposed as an extra postulate.

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 Q7. De Broglie’s Equation. Significance of this Equation

λ = h/mv = h/p

Symbol Meaning
λ Wavelength of matter wave
h Planck’s constant (6.626 × 10−34 J·s)
m, v, p Mass, velocity, momentum of particle

Derivation

From Einstein’s mass-energy relation: E = mc2 .

From Planck’s relation: E = hν = hc/λ.
Equating the two: mc2 = hc/λ ⇒ λ = h/mc = h/p. Replacing c with v for any massive particle gives
the general de Broglie relation, λ = h/mv.

Significance

1. Every moving particle has an associated matter wave.

2. The wave nature is significant only for very small (subatomic) masses, since large mass gives an
extremely small λ.
3. It naturally explains Bohr’s quantization condition.
4. It led to the invention of the electron microscope.
5. It forms the foundation of quantum mechanics.

Q8. Schrödinger Equation and the Hamiltonian Operator

The Schrödinger Wave Equation

∇2 ψ + (8π 2 m/h2 )(E − P.E.)ψ = 0

Derivation

Step 1: Start with the wave function ψ = A sin(2πx/λ).

Step 2: Taking the second derivative:
d2 ψ/dx2 = −(4π 2 /λ2 )ψ . . . (1)

Step 3: From de Broglie’s relation, λ = h/mv, so λ2 = h2 /m2 v 2 .

Step 4: Kinetic energy: K.E. = 21 mv 2 = E − V , so m2 v 2 = 2m(E − V ).
Step 5: Substituting into equation (1):
d2 ψ/dx2 = −(4π 2 · 2m(E − V )/h2 )ψ

d2 ψ/dx2 + (8π 2 m/h2 )(E − V )ψ = 0

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Hamiltonian Operator

The Schrödinger equation may be written compactly as:

Ĥψ = Eψ

where Ĥ is the Hamiltonian operator:

Ĥ = −(h2 /8π 2 m)∇2 + V

It represents the total energy operator, equal to the sum of the kinetic energy operator and the potential
energy operator.

Q9. Significance of Ψ and Ψ2

Significance of Ψ (Wave Function)

1. ψ is a mathematical function describing the quantum state of a particle.

2. ψ itself has no direct physical meaning.
3. ψ may be positive, negative, or even complex.
4. ψ must be single-valued, finite, continuous, and normalizable.

Significance of Ψ2 (Probability Density)

1. ψ 2 gives the probability density of finding the electron at a point.

2. ψ 2 is always positive and real.
3. ψ 2 dV is the probability of finding the electron within volume element dV .
Z
ψ 2 dV = 1 (Normalization condition)

This condition states that the electron must be somewhere in space, so the total probability over all
space equals 1.

Q10. Particle in One-Dimensional Box

Setup

A particle of mass m is confined in a box of length a. Inside the box (0 < x < a), V = 0. Outside the
box, V = ∞, so ψ = 0 there.

Schrödinger Equation Inside the Box (V = 0)

d2 ψ/dx2 + (8π 2 mE/h2 )ψ = 0

Let k 2 = 8π 2 mE/h2 , giving: d2 ψ/dx2 + k 2 ψ = 0

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Solution and Boundary Conditions

General solution: ψ = A sin kx + B cos kx

At x = 0: ψ = 0 ⇒ B = 0, so ψ = A sin kx
At x = a: ψ = 0 ⇒ sin ka = 0 ⇒ ka = nπ, so k = nπ/a

Normalized Wave Function

p
ψn = 2/a sin(nπx/a)

Fig 10.1: Wave functions ψn (left) and probability

densities ψn2 (right) for n = 1, 2, 3

Q11. Expression of Minimum Energy E for Particle in One-Dimensional Box

Derivation

From k = nπ/a and k 2 = 8π 2 mE/h2 :

n2 π 2 /a2 = 8π 2 mE/h2

En = n2 h2 /8ma2

Minimum Energy (Zero-Point Energy)

Since n cannot be zero (otherwise ψ = 0 everywhere, the trivial solution), the lowest allowed value is
n = 1:
Emin = E1 = h2 /8ma2

This is called the Zero-Point Energy. Even at absolute zero, the particle retains this minimum energy
— a purely quantum mechanical result with no classical analogue.

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 Fig 11.1: Quantized energy levels for a particle in a box

Q12. Expression for Particle in Three-Dimensional Box

Setup

Box dimensions ax , ay , az along the x, y, z axes respectively. V = 0 inside the box and V = ∞ outside.

Fig 12.1: A three-dimensional potential box

Schrödinger Equation (V = 0)

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 ∂ 2 ψ/∂x2 + ∂ 2 ψ/∂y 2 + ∂ 2 ψ/∂z 2 + (8π 2 m/h2 )Eψ = 0

Variable Separation

Let ψ = ψx · ψy · ψz , leading to three independent one-dimensional equations.

Normalized Wave Function

p
ψ= 8/ax ay az · sin(nx πx/ax ) · sin(ny πy/ay ) · sin(nz πz/az )

Energy Expression

h i
E = (h2 /8m) n2x /a2x + n2y /a2y + n2z /a2z

For a cubic box (ax = ay = az = a):

E = (h2 /8ma2 )(n2x + n2y + n2z )

Degeneracy

Different combinations of (nx , ny , nz ) can give the same total energy. These states are called degen-
erate. Example: (2, 1, 1), (1, 2, 1), (1, 1, 2) all give E = 6h2 /8ma2 — this is a triply degenerate
state.

Q13. Quantum Numbers and Atomic Wave Function

The Four Quantum Numbers

Quantum Number Symbol Values Describes

Principal n 1, 2, 3 . . . Shell, energy, size
Azimuthal l 0 to (n − 1) Subshell, shape
Magnetic m −l to +l Orbital orientation
Spin s + 12 , − 12 Electron spin

Atomic Wave Function

ψ(r, θ, ϕ) = R(r) · Θ(θ) · Φ(ϕ)

• R(r) — Radial function (depends on n, l)

• Θ(θ) — Polar angular function (depends on l, m)
• Φ(ϕ) — Azimuthal angular function (depends on m)

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 Fig 13.1: Characteristic angular shapes of s, p,
and d orbitals

Q14. Radial Function, Angular Function, Radial Distribution Function, Nodal

Surfaces

Radial Function R(r)

Describes how ψ varies with distance r from the nucleus. It determines the size of the orbital. R2 gives
the radial probability density.

Angular Function

Describes how ψ varies with angles θ and ϕ. It determines the shape and orientation of the orbital,
giving rise to the characteristic shapes of s, p, d orbitals.

Radial Distribution Function

4πr2 ψ 2 = 4πr2 R2

This gives the probability of finding the electron within a thin spherical shell of radius r. The function
always starts at (0, 0), and its peak indicates the most probable distance of the electron from the nucleus.

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 Fig 14.1: Radial
distribution functions for 1s, 2s, 2p, 3s, 3p, 3d orbitals

Radial Nodes

Number of Radial Nodes = n − l − 1

Orbital n l Radial Nodes
1s 1 0 0
2s 2 0 1
2p 2 1 0
3s 3 0 2
3p 3 1 1
3d 3 2 0

Nodal Surfaces

A nodal surface is a region where ψ = 0, meaning the probability of finding the electron there is zero.
There are two types:
1. Radial nodes — spherical surfaces at certain values of r.
2. Angular nodes — planar or conical surfaces; their number equals l.
Total Nodes = (n − l − 1) + l = n − 1

Orbital Radial Nodes Angular Nodes Total Nodes

1s 0 0 0
2s 1 0 1
2p 0 1 1
3s 2 0 2
3p 1 1 2
3d 0 2 2

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End of Chapter 1 — Quantum Mechanics

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