Solid State Physics
Exam Preparation Notes
2 Most Important Questions — Full Answers
Papers 7477 ([Link]. Physical Sc. DSE) · 5870 ([Link]. Prog. NEP UGCF-2022)
Subject Solid State Physics — Semester VI
Max Marks 75 (paper 7477) · 60 (paper 5870)
Coverage Questions 4 & 7 (paper 7477) · Q3 & Q4 (paper 5870)
Question 1 — Kronig-Penney Model & Energy Bands
Appears in Paper 7477 — Q7 (a)(b) | Paper 5870 — Q3 (a)(b)
Marks 15 marks total (typical)
Type Derivation + explanation + diagram
1.1 What is the Kronig-Penney Model?
The Kronig-Penney model is a one-dimensional quantum mechanical model that explains the formation of
energy bands in crystalline solids. It replaces the real periodic crystal potential with an idealized periodic
square-well potential — alternating wells (width a, potential V = 0) and barriers (width b, height V0).
Despite its simplicity, it reproduces the key feature of real band structure: allowed energy bands separated
by forbidden gaps.
Periodic potential: V(x) = 0 for 0 < x < a (well region)
V(x) = V■ for −b < x < 0 (barrier region)
Period of lattice: (a + b)
1.2 Bloch's Theorem (Starting Point)
Since the potential is periodic, by Bloch's theorem the wavefunction must satisfy:
psi(x + a + b) = eik(a+b) psi(x)
where k is the Bloch wave vector. The Schrodinger equation is solved separately in each region, then
matched at the boundaries using continuity of psi and dpsi/dx.
1.3 The Kronig-Penney Equation (Main Result)
After applying boundary conditions and Bloch periodicity, the transcendental equation relating energy E to
wave vector k is:
cos(ka) = P [sin(alpha*a) / (alpha*a)] + cos(alpha*a)
where: alpha = sqrt(2mE) / h-bar (wave vector inside the well) P = m*V■*b*a / h-bar² = Potential Barrier
Strength k = Bloch wave vector
Physical significance: The left-hand side lies between −1 and +1. For values of E where the right-hand
side exceeds this range, no real k exists — these energies are forbidden (energy gaps). Where the right
side lies within [−1, +1], real k values exist — these are allowed bands.
1.4 Special Case: P << 1 (Weak Barriers) — Derivation at k = 0
When the barrier strength P is very small, we can expand sin(alpha*a) for small alpha*a using the Taylor
approximation:
sin(alpha*a) / (alpha*a) approx 1 - (alpha*a)²/6
cos(alpha*a) approx 1 - (alpha*a)²/2
Substituting into the Kronig-Penney equation:
cos(ka) = P[1 - (alpha*a)²/6] + 1 - (alpha*a)²/2
At k = 0, cos(ka) = 1, so:
1 = P - P(alpha*a)²/6 + 1 - (alpha*a)²/2
0 = P(alpha*a)²/6 + (alpha*a)²/2 ... but for P << 1, the second term dominates:
E = h² P / (4π² m a²)
This is the energy of the lowest band at k = 0 when P << 1. It shows that energy increases with P
(stronger barriers = higher band energy) and decreases with a (wider wells = lower energy).
1.5 Effect of Barrier Strength P on Band Width
Condition Allowed Band Width Forbidden Gap Width Behaviour
P→0 Very wide Free electron
Zero
(no barriers) (continuous) parabola E = h²k²/2m
Small P Nearly free
Wide allowed bands Narrow gaps
(weak barrier) electron model
Large P Tight-binding
Narrow allowed bands Wide forbidden gaps
(strong barrier) (atomic) limit
P→∞ Zero width Isolated atoms
Infinite gaps
(infinite barriers) (discrete levels) (bound states)
1.6 Classification of Solids Based on Energy Bands
Solid Type Band Structure Band Gap Example
Highest band partially
Conductor
filled OR two bands None / Zero Cu, Na, Al
(Metal)
overlap
Valence band full;
Small Si (~1.1 eV)
Semiconductor conduction band empty
~0.1 to 3 eV Ge (~0.67 eV)
at 0 K
Valence band full; Large Diamond
Insulator
conduction band empty > 5 eV (~5.5 eV)
Key points to remember: (1) Gaps always open at Brillouin zone boundaries k = n*pi/a. (2) Width of the
forbidden gap increases with P. (3) The number of allowed energy states in each band equals 2N
(including spin) where N = number of unit cells. (4) Effective mass m* = h-bar² / (d²E/dk²) differs from rest
mass because the electron feels the periodic potential.
Question 2 — Specific Heat of Solids: Dulong-Petit,
Einstein & Debye
Appears in Paper 7477 — Q4 (full 15-mark question) | Paper 5870 — Q4 (b)
Marks 15 marks — most marks-per-topic in both papers
Type Full derivation + assumptions + temperature dependence + comparison
2.1 Classical Law: Dulong-Petit (1819)
The classical treatment uses the equipartition theorem: each degree of freedom contributes (1/2)kBT to
the average energy. A 3D harmonic oscillator has 3 kinetic and 3 potential degrees of freedom, so each
atom has average energy 3kBT.
Total internal energy for N atoms: U = 3N kBT
Molar specific heat at constant volume:
CV = dU/dT = 3NkB = 3R approx 24.9 J/mol.K
This is the Dulong-Petit law. R = 8.314 J/mol.K is the gas constant. It works well for most solids at room
temperature and above, but fails at low temperatures where CV drops toward zero experimentally.
2.2 Assumptions of Einstein's Model (1907)
1. A solid of N atoms consists of 3N independent harmonic oscillators (one per degree of freedom).
2. All 3N oscillators vibrate at the same angular frequency omega_E (the Einstein frequency). This is
the key simplification.
3. Each oscillator is quantized: allowed energies are E_n = (n + 1/2) h-bar omega_E, where n = 0, 1,
2, ...
4. Oscillators obey Bose-Einstein statistics (Planck distribution).
2.3 Derivation of Einstein's Specific Heat Formula
Step 1 — Average energy of one quantum oscillator (Planck):
= h-bar*omega_E / [exp(h-bar*omega_E / k_B*T) - 1] + h-bar*omega_E/2 (ZPE)
Step 2 — Total internal energy of 3N oscillators (ignoring constant ZPE):
U = 3N * h-bar*omega_E / [exp(theta_E/T) - 1]
where the Einstein temperature theta_E = h-bar*omega_E / k_B (material-specific constant, typically
100-300 K).
Step 3 — Differentiate U with respect to T:
CV = dU/dT = 3NkB (theta_E/T)2 * exp(theta_E/T) / [exp(theta_E/T) - 1]2
This is the Einstein formula for specific heat of solids.
2.4 Temperature Dependence — Two Limiting Cases
Limit Condition Approximation Result Agrees?
High T T >> theta_E C<sub>V</sub> -> 3Nk<sub>B</sub> = 3R
(theta_E/T)<super>2</super> * e<super>x</super>/(e<super>x</super>-1)<super>2</sup
YES
(classical) exp(theta_E/T) approx 1 + theta_E/T (Dulong-Petit)
Low T T << theta_E C<sub>V</sub> proportional
PARTIAL
to e<super>-theta_E/T</super
(theta_E/T)<super>2</super> * e<super>-theta_E/T</super>
(quantum) exp(theta_E/T) >> 1 (drops exponentially) (too fast)
2.5 Limitation of Einstein's Model and Debye's Correction
Einstein's failure at very low T: Experiments show CV proportional to T3 at low temperatures, but
Einstein's formula predicts an exponential drop exp(-theta_E/T). The reason: Einstein's single-frequency
assumption is too rigid. Real crystals have a spectrum of vibrational frequencies (phonon modes)
ranging from zero up to a maximum Debye frequency nu_D.
Debye's improvement (1912):
Replaces the single Einstein frequency with a continuous distribution of frequencies g(omega)
proportional to omega2, cut off at the Debye frequency omega_D. This gives:
CV proportional to T3 for T << theta_D (Debye T3 law)
CV -> 3R for T >> theta_D (Dulong-Petit recovered)
The Debye model matches experiments extremely well across the full temperature range, especially the
T3 behaviour at low T that Einstein could not capture.
2.6 Quick Comparison: Classical vs Einstein vs Debye
Dulong-Petit Einstein Debye
Feature
(Classical) Model Model
Year 1819 1907 1912
Continuous Single fixed Spectrum
Oscillator freq.
(classical) freq. nu_E 0 to nu_D
Maxwell- Bose-Einstein Bose-Einstein
Statistics
Boltzmann (Planck) (Planck)
High T limit 3R (correct) 3R (correct) 3R (correct)
Exponential
Low T limit 3R (WRONG) T3 (CORRECT)
(partial)
Agreement Good, fails Excellent
Only high T
with experiment at very low T all T
Exam tips for Q2: Always state all 4 assumptions before starting the derivation. Show both high-T and
low-T limits — these are often separately marked. Draw a rough CV vs T curve showing the classical
plateau at 3R, the Einstein/Debye rise, and the T3 region. Mention that Debye corrects Einstein by using
a phonon frequency spectrum instead of a single frequency.