Thermal Properties of Solids: Debye's Model: Pradeep Thakur

Thermal properties of solids:
Debye’s model
Pradeep Thakur
College of Engg., Pune
August 3, 2022
Pradeep Thakur (College of Engg., Pune) Thermal properties of solids: Debye’s model August 3, 2022 1 / 20
1 Background
2 Debye’s model of specifc heat
3 Numerical problems
Background
Dulong-Petit Law: the molar specific heat is a constant

Cv = 3Nk = 3R ≈ 24.93 J/mol
Law fails at low temperature; C decreases as temperature is decreased

Einstein assumed each atom to be an independent quantum oscillator,
vibrating at fixed angular frequency ω
3Nℏω eβℏω ℏω/kB T 2

∂⟨E ⟩
Cv = = 2
(1)
∂T V (eβℏω − 1)
2
θE eθE /T
∴ Cv = 3NkB 2 (2)
T eθE /T − 1
ℏω
where θE = kB is called the “Einstein characteristic temperature”
Background
Dulong-Petit Law: the molar specific heat is a constant

Cv = 3Nk = 3R ≈ 24.93 J/mol
Law fails at low temperature; C decreases as temperature is decreased

Einstein assumed each atom to be an independent quantum oscillator,
vibrating at fixed angular frequency ω
3Nℏω eβℏω ℏω/kB T 2

∂⟨E ⟩
Cv = = 2
(1)
∂T V (eβℏω − 1)
2
θE eθE /T
∴ Cv = 3NkB 2 (2)
T eθE /T − 1
ℏω
where θE = kB is called the “Einstein characteristic temperature”
Background
Assumptions of Einstein’s model of specific heat of a solid:

(1) All atoms, numbering N (Avogadro number), are noninteracting
quantum-mechanical simple-harmonic oscillators (SHOs)
(2) Frequency of oscillation is the same for all oscillators
∴ Energy levels of each 1d mode of an oscillator are quantized:

1 h
εn = n + ℏω; ℏ = ; ω = 2πν (3)
2 2π
Debye discarded assumption 2.

He also removed the “noninteracting” part of assumption 1.
So, in effect, he allowed the oscillators to interact with each other
Since each atom’s vibrations can be characterized by 3 “normal” modes of
vibration, N atoms will have 3N normal modes of vibration.
At low energies, these mutually influencing vibrations of atoms form
collective excitations - sound waves - medium is not continuous
These collective excitations are quantized bosons - phonons!
Debye’s model of specifc heat
Debye’s model
Debye’s model still has 3N normal modes, like Einstein’s
But they are now 3N normal modes of the collective excitations of the
lattice, not the normal modes of independent oscilators
3N normal modes of the phonons
Phonons = quantized lattice vibrations, having energy ℏω
(quantum number, n, absorbed into ω and 21 renormalized to zero in Eq.
(3))
Phonons are bosonic “quasi-particles”, whose number is not conserved, so
chemical potential associated with the “phonon gas” is zero
∴ Mean number of photons with energy ℏω:
1
⟨n(ω)⟩ = (4)
e βℏω − 1
We want to find mean energy and then its temperature-derivative,
but instead of using the partition function, we will assume frequency is a
continuous variable and use an integral with the density of states ...
Total energy of the phonon gas is

Z ω2
E= ℏω ⟨n(ω)⟩ D(ω) dω (5)
ω1
D(ω) : density of states = no. of frequencies in range ω and ω+dω;

ω1 : lower limit of frequency = ?
ω2 : upper limit of frequency = ?

Z ω2
E= ℏω ⟨n(ω)⟩ D(ω) dω (5)
ω1
D(ω) : density of states = no. of frequencies in range ω and ω+dω;

ω1 : lower limit of frequency = ?
ω2 : upper limit of frequency = ? Lower limit will be zero, since no
oscillation is the smallest oscillation possible ⇒ ω1 = 0
Upper limit of the frequency is not infinity (WHY?), but a finite value and
is termed the Debye frequency, ωD .
Z ωD
E= ℏω ⟨n(ω)⟩ D(ω) dω (6)
0
How to determine ωD ?
Total number of normal modes (allowed states) of the solid is

Z ωD
D(ω) dω = 3N (7)
0
So D(ω) is the main quantity that needs to be determined.
How? (Ref.: C. Kittel, Ch. 5 - Phonons II . Thermal properties)
We have seen earlier in the 1d particle-in-a-box problem that fixed
boundary condition gives stationary wave solutions (∝ sin(kx)) of the
Schrödinger equation, whereas periodic boundary condition gives
plane-wave solutions ∝ exp(ikx)
Fixed boundary condition: ψ(x = 0) = ψ(x = L) = 0
Periodic boundary condition: ψ(x = 0) = ψ(x = L)
∴ in a 3d crystal of length L, ⃗k is determined by the condition
exp [i(kx x + ky y + kz z)] = exp {i [kx (x + L) + ky (y + L) + kz (z + L)]}
√3
2π 4π Nπ
∴ kx , ky , kz = 0; ± ; ± ; · · · ; ± . (8)
L L L
√
where one side of the cube is L = 3 N × lattice constant
√
3
2π 4π Nπ
kx , ky , kz = 0; ± ; ± ; · · · ; ±
L L L
2π
Unit volume in k-space is a cube of side L , with one k-value in it
√
3
Total volume is cube of side 2kmax , where kmax = N π
L .
∴ No. of modes (or no. of k-values) with wavevector < k is
3
N = (volume in k-space) ÷ 2π L
Now, we approximate total volume in k-space by a sphere of radius k,
such that k 2 = kx2 + ky2 + kz2 .
So Cartesian coordinates → spherical polar coordinates
3
∴ Total modes in sphere of radius k = N = 43 πk 3 ÷ 2π L
3 polarization states: 2 transverse, 1 longitudinal
L3 k 2 dk
∴ Density of states per polarization state, D 1 (ω) = dNdω = 2π 2 dω
3 2 dk
∴ Total density of states in frequency range dω, D(ω)dω = 3 L2πk2 dω dω
the prefactor 3 denoting the number of polarization states
In Debye’s approximation, the velocity of sound in the solid is taken

to be a constant vs , just as in a classical solid.
In a classical solid, the classical wave equation is
∂2f ∂2f ∂2f 1 ∂2f

+ + =
∂x 2 ∂y 2 ∂z 2 vs2 ∂t 2
where vs is the velocity of the sound wave.

λ ω
vs = νλ = (2πν) × =
2π k
ω dk 1
∴ k = , and = (9)
vs dω vs
L3 k 2 dk 3V ω 2
∴ Total DOS, D(ω)dω = 3 2 dω = 2 3 dω, with V = L3
2π dω 2π vs
3V ω 2
∴ D(ω)dω = dω (10)
2π 2 vs3
The sound wave is composed of two transverse modes of vibration and one
longitudinal mode of vibration, moving with velocities vT and vL
respectively. vs is the effective sound velocity.
V ω2 V ω2
DL (ω) dω = ; D T (ω) dω = 2 (11)
2π 2 vL3 2π 2 vT3
∴ We can rewrite Eq. (10) as
D(ω) dω = (DL (ω) + DT (ω))dω

V ω2 1

2
⇒ D(ω) dω = + dω (12)
2π 2 vL3 vT3
Z ωD Z ωD 3
V ωD 1 2
∴ D(ω) dω = (DL (ω) + DT (ω))dω = 3
+ 3 (13)
0 0 6π 2 vL vT
where,

3 1 2
≡ 3
+ 3 (14)
vs3 vL vT
∴ From Eq. (7),
ωD ωD 3
3V ω 2
Z Z
V ωD 3
3N = D(ω) dω = dω = (15)
0 0 2π 2 vs3 6π 2 vs3
3
V ωD

1 2
∴ 3N = 3
+ 3
6π 2 vL vT
−1
18Nπ 2

3 1 2
⇒ ωD = 3
+ 3 (16)
V vL vT
Debye spectrum (Fig. from F. Reif, Sec. 10.2)
Using Eqs. (12) and (16), we obtain the Debye spectrum:

9Nω 2
(
3
ωD
for ω < ωD
D(ω) = (17)
0 for ω > ωD
Now that we know the DOS, we can determine ⟨E ⟩ and CV .
Z ωD
⟨E ⟩ = ℏω ⟨n(ω)⟩ D(ω) dω
0
Z ωD
1 9N 2
= ℏω ℏω/k T 3
ω dω
0 e B − 1 ωD
9Nℏ ωD ω3
Z
∴ ⟨E ⟩ = 3 dω (18)
ωD 0 e ℏω/kB T − 1
9Nℏ kT 4 ℏωD /kT x 3
Z
ℏω
∴ ⟨E ⟩ = 3 x
dx; x = (19)
ωD ℏ 0 e − 1 kT
ℏωD
Define the Debye characteristic temperature, θD = .
kB
θD /T
9NkT 4 x3
Z
∴ ⟨E ⟩ = 3
dx (20)
θD 0 ex − 1
In terms of original parameters, from Eq. (18), we have
9Nℏ ωD ω3
Z
⟨E ⟩ = 3 dω (21)
ωD 0 e ℏω/kB T − 1
Differentiating the above Eq. w.r.t. T , & using Eq.(15), one gets · · ·
3 Z xD
x 4 ex

T
CV = 9 N kB dx (22)
θD 0 (e x − 1)2
θD
where xD = T , and x = ℏω/kB T .
Question: Verify that for T ≫ θD Dulong-Petit’s law is obtained.

(Clue: θTD is small, so e x ≈ 1 + x).
Thus, for temperatures greater than the Debye temperature, the
lattice behaves classically.
For T ≪ θD , θD → ∞, so
θD /T ∞
x3 x3
Z Z
π
dx = dx =
0 ex − 1 0
x
e −1 15
9NkT 4 π 3 π 4 NkB 4
∴ ⟨E ⟩ = 3
⇒ ⟨E ⟩ = 3
T (23)
θD 15 5 θD
3
12 T
∴ CV = π 4 NkB (24)
5 θD
⇒ CV ∝ T 3
This is the exact behaviour of molar specific heat observed at low

temperatures!
Expt. and Debye theory at low T
F. Reif, Fundamentals of Statistical and Thermal Physics,

Section 10.2 - Debye approximation
More remarks on the Debye model
1. Eqs. (22) and (26) indicate that the dependence of CV on T /θD

should be the same for all monatomic solids, even though θD is different
for different solids.
2.. At high temperatures, forces between atoms are no longer harmonic;
phonons interact strongly with each other.
3. Even at intermediate temperatures, the Debye approximation fails.
4. However, exact low-T behaviour!
Useful constants and expressions

1 amu = 1.67 × 10−27 kg
ℏ = 1.054 × 10−34 J s; h = 6.62 × 10−34 J s
kB = 1.38 × 10−23 J K −1
NA = 6.02 × 1023 mol −1
R = kB NA = 8.31 J mol −1 K −1
12
(CV )Debye = π 4 R (T /θD )3 at low temperatures
5
hνD
θD = ℏωkB
D
= kB = Debye temperature
General expressions:
T 3 ωD x3
Z
⟨E ⟩ = 9 N kB T dx x ; N is no. of atoms; xD = θD /T
θD 0 e −1
3 Z ωD
T x 4 ex
CV = 9 N kB dx x , with x = ℏω/kB T
θD 0 (e − 1)2
Numerical problems
Numerical Problems
1. Calculate the electronic specific heat of kmol of copper at 300K. At

what low temperature is the lattice specific heat (Debye) of copper equal
to this electronic specific heat? The Fermi energy of copper is 7ev and θD
for copper is 348K . Electronic molar specific heat for a metal is
(π 2 R/2)(kB T /EF ).
2. In aluminium, vL = 6.32 × 103 m/s and vT = 3.1 × 103 m/s.

ρAl = 2.7 × 103 kg /m3 and its atomic weight is 26.97. (a) Calculate νD for
aluminium with these data. (b) θD for aluminium as obtained from sp.
heat measurements is 375K . Find νD for this value, and compare it with
the result obtained in (a). (c) Are the preceding values consistent with the
vibrational frequency of aluminium atoms in solid aluminium? (For
comparison, standard value of vibrational frequency of aluminium atom is
6.4 × 1012 s −1 .)
Numerical problems
3. The Debye temperature of carbon (diamond structure) is 1850K . (a)

Calculate the specific heat per kmol for diamond at 20K . (b) Also
compute the highest lattice frequency (νD , not ωD ) involved in the Debye
theory.
(Ans. (a) CV = 2.45J kmol −1 s −1 , (b) νD = 3.85 × 1013 s −1 )
4. Calculate the Debye specific heat of copper at (a) 10K , and at (b)
300K , given that νD = 6.55 × 1012 s −1 .
(Ans. (a) 62.67 J kmol −1 K −1 , (b) 1.6 × 103 kJ kmol −1 K −1 )
5. Estimate the Debye temperature of gold if its atomic weight is 197

amu, density is 1.9 × 104 kg /m3 and the velocity of sound is 2100 m/s.
(Ans. 240 K )

Thermal Properties of Solids: Debye's Model: Pradeep Thakur

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Thermal properties of solids:

College of Engg., Pune

2 Debye’s model of specifc heat

Dulong-Petit Law: the molar specific heat is a constant

Law fails at low temperature; C decreases as temperature is decreased

3Nℏω eβℏω ℏω/kB T 2

Dulong-Petit Law: the molar specific heat is a constant

Law fails at low temperature; C decreases as temperature is decreased

3Nℏω eβℏω ℏω/kB T 2

Assumptions of Einstein’s model of specific heat of a solid:

Debye discarded assumption 2.

Total energy of the phonon gas is

D(ω) : density of states = no. of frequencies in range ω and ω+dω;

Total energy of the phonon gas is

D(ω) : density of states = no. of frequencies in range ω and ω+dω;

Total number of normal modes (allowed states) of the solid is

In Debye’s approximation, the velocity of sound in the solid is taken

∂2f ∂2f ∂2f 1 ∂2f

∴ We can rewrite Eq. (10) as

D(ω) dω = (DL (ω) + DT (ω))dω

Debye spectrum (Fig. from F. Reif, Sec. 10.2)

Using Eqs. (12) and (16), we obtain the Debye spectrum:

Now that we know the DOS, we can determine ⟨E ⟩ and CV .

In terms of original parameters, from Eq. (18), we have

Question: Verify that for T ≫ θD Dulong-Petit’s law is obtained.

This is the exact behaviour of molar specific heat observed at low

Expt. and Debye theory at low T

F. Reif, Fundamentals of Statistical and Thermal Physics,

More remarks on the Debye model

1. Eqs. (22) and (26) indicate that the dependence of CV on T /θD

Useful constants and expressions

1. Calculate the electronic specific heat of kmol of copper at 300K. At

2. In aluminium, vL = 6.32 × 103 m/s and vT = 3.1 × 103 m/s.

3. The Debye temperature of carbon (diamond structure) is 1850K . (a)

5. Estimate the Debye temperature of gold if its atomic weight is 197

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