Kinetic theory of gases

for ideal monatomic gas of N molecules

energy U = N 1/2mvrms2
pressure P = d(mv)/dt A = N 1/3mvrms2 V
observe P V = N kB T
Boltzmann constant kB relates T to energy

equipartition of energy: 1/2kBT for each d.o.f

1/2mvrms2 = 3/2kBT where vx,rms2 = 1/3vrms2

molar specific heat Cv = U/T = 3/2R

gas constant R = kBNA

diatomic gas has 3 trans., 2 rot. and 2 vib. d.o.f

where 2 vib. d.o.f are kinetic and potential
molar specific heat Cv = U/T = 7/2R
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Kinetic theory of crystals

for ideal monatomic cubic crystal of N atoms

energy U = N (1/2mvrms2 + 1/2(x-a)rms2)
equipartition of energy: 1/2kBT for each d.o.f
atom in crystal vib. d.o.f. =6 (3xKE+3xPE)
molar specific heat Cv = U/T = 3R

this model is too simple:

quantum description of vibrations
CV 0 as T 0

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anharmonic potential
U = 1/2k(x-a)2 - c(x-a)3 ...

Vibrations of monatomic lattice in 1D

positions xj=ja and displacements xjxj+uj
assume force due to nearest neighbours
Fj = (uj+1 - uj) - (uj - uj-1) = (uj+1 + uj-1 - 2uj)

assume wave solution uj=Aexp(i(kxj-t))

wavevector k=2/ and angular frequency =2f

Fj = maj hence d2uj/dt2 = -2uj

satisfied if 2=(/m) [2- uj+1/uj - uj-1/uj]
use uj+1/uj=exp(ika) and uj-1/uj=exp(-ika)
2 = (/m) [2 - exp(ika) - exp(-ika)] = 2(/m) [1 - cos(ka)] = 4(/m) sin2(ka/2)

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= maxsin(ka/2) with max

=2(/m)1/2

at rest

k has continuous values and k denotes direction

for large , have k0 and sin(ka/2)ka/2

=2(k/m)1/2ka/2
wave velocity v0=/k=a(/m)1/2
group velocity v=d/dk=v0
(atoms in phase)
elastic wave: v=(B/)1/2, B=a, =m/a

k<</a, in phase

1st Brillioun zone

for small , have max as k/a

group velocity v=d/dk=v0cos(ka/2)
group velocity0 as k/a
(atoms in antiphase)

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 the first Brillioun zone: -/a<k</a

is a region in the reciprocal lattice
halfway to reciprocal lattice points K=2/a

note: uj(k+K)=exp(iKxj)uj(k)=uj(k)
if K is a reciprocal lattice vector
because Kxj=n and exp(iKxj)=1
k>/a is equivalent to k'=k-K and -/a<k'<0
k<-/a is equivalent to k'=k+K and 0<k'</a

the Brillioun zone describes all unique waves

wave with k=/a is standing wave due to Bragg reflection
2dsin= with d=a and 2=180 hence k=2/=/a

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at rest
k=/a, out of phase

 wave solutions uj=sexp(i(k.rj-st))

where s and s depend on wavevector k

angular frequency s(k) is function in 3D

3 polarisation vectors s(k)

simplified for special geometries

1 longitudinal (L), with u parallel to k
2 transverse (T), with u perpendicular to k
referred to as T/L "modes" or "branches"

in general s have mixture of T/L

s(k) are different for L and T modes
L involves stretching of bonds, higher
T involves bending of bonds, lower
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3D dispersion s(k)
consider s(|k|) for a particular direction k^
specified by reciprocal lattice vector K, e.g. (1,0,0)

s(|k|) has similar behaviour to 1D crystal

for large , have |k|0 and find =v0|k|

wave velocity = group velocity = v0
(atoms in phase)
for small , have max as |k||K|/2
standing wave due to Bragg reflection
(atoms in antiphase)

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Vibrations of diatomic lattice in 1D

positions xj=ja/2 and displacements xjxj+uj
even j for atom type M
odd j for atom type m

assume force due to nearest neighbours

Fj = (uj+1 - uj) - (uj - uj-1) = (uj+1 + uj-1 - 2uj)

for even j, assume wave solution uj=Aexp(i(kxj-t))

for odd j, assume wave solution uj=Bexp(i(kxj-t))

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 Fj=Maj satisfied if -M2uj = [uj+1/uj + uj-1/uj - 2]

hence -M2 = [Bexp(ika/2)/A + Bexp(-ika/2)/A - 2] = [2Bcos(ka/2)/A - 2]

Fj=maj satisfied if -m2uj = [uj+1/uj + uj-1/uj - 2]

hence -m2 = [Aexp(ika/2)/B + Aexp(-ika/2)/B - 2] = [2Acos(ka/2)/B - 2]

require (2 - M2)(2 - m2) = 42cos2(ka/2)

this is quadratic in 2 with 2 solutions

2 =
( + ) 2 4 sin 2 ( / 2 )
( + )

1/ 2

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 ( + )
( + )
4 sin ( / 2 )

=

1/ 2

for large , have k0 and sin(ka/2)ka/2 with ka/2<<1

can rearrange to get two solutions

low frequency solution =v0k

wave velocity = group velocity = v0 = (a2/2(M+m))1/2
same as for monatomic lattice in 1D
called acoustic (like sound waves)

high frequency solution =(2(M+m)/Mm)1/2

group velocity=0
called optical (because interact with photons)

for small, have k/a with sin(ka/2)1

can rearrange to get two solutions, 2=2/M or 2/m
group velocity=0
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Vibrations of diatomic lattice in 3D

as for the monatomic lattice in 3D
wave solutions uj=sexp(i(k.rj-st))

dispersion s(k) is function in 3D

consider s(|k|) for a particular direction k^

3 polarisation vectors s(k)

1 longitudinal (L) and 2 transverse (T)

as for diatomic lattice in 1D

M and m atoms can vary in phase

low frequency solution

called acoustic (M and m atoms in phase)

high frequency solution

called optical (M and m atoms out of phase)
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Classical approach
energy of atom in 1-dimension E = 1/2mvx2 + 1/2kx2
need 3 dimensions in total

average over Boltzmann distribution

<E> = Eexp(-E/kBT)dvdx / exp(-E/kBT)dvdx
gives <E> = kBT
i.e. equipartition of energy: 1/2kBT for each d.o.f.

hence U = 3NkBT or CV = 3NKB = 3R

gas constant R = kBNA

agrees with experiment at high T but not at low T

wrong because doesn't include quantisation of E
due to quantum mechanics

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Quantum mechanics approach

Planck proposed electromagnetic wave E=n*
Einstein proposed n photons with E=
vibrational waves are quantised as phonons**

** Note: phonons used

in spectroscopy lectures

energy of vibrational wave is n

i.e. n phonons each with energy

corresponds to Bose-Einstein distribution

phonons are a type of boson (integer spin)
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probability

average over quantised energies

<E> = n En exp(-En/kBT) / n exp(-En/kBT)
gives <E> = / [exp(/kBT) - 1] = <n>
<n> = 1 / [exp(/kBT) - 1]

* Note: QM of simple
harmonic motion
solutions are quantised
with E=(n+1/2)

Maxwell-Boltzman
Bose-Einstein
Fermi-Dirac

energy

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Einstein model

(like an optical vibration)
total of 3N different vibrational modes

hence U = 3NE / [exp(E/kBT) - 1]

CV = 3NKB FE(E,T), with function FE

temperature dependence of CV due to FE

FE(E,T) =
(E/kBT)2 exp(E/kBT) / [exp(E/kBT) - 1]2

FE(E,T) 1 at high T

because exp(E/kBT)1+E/kBT

FE(E,T) (E/kBT)2exp(-E/kBT) for T<<TE

where Einstein temperature TE=E/kB

does not agree with experiment

because experimental CV proportional to T3 at low T
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Debye model

(like an acoustic vibration)
total of 3N different vibrational modes

* g(E) = 3N
in Einstein model

U = g() / [exp(D/kBT) - 1] d
density of states g()*
gives number of modes at each
require g() d = 3

find g() = 3V2 / 22v03 for 0<<D

3N = VD3 / 22v03
U=
[3V / 22v03] 3 / [exp(D/kBT) - 1] d
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 U = [3V / 22v03] 3 / [exp(D/kBT) - 1] d

change to dimensionless variable x=(/kBT)

U = [9NKBT4 / D3] x3 / [exp(x) - 1] dx

where Debye temperature D = TD = D/kB

CV = [9NKBT3 / D3] x4 exp(x) / [exp(x) - 1]2 dx

integral 1/3(D/T)3 at high T
integral 4/15 at low T

CV = [124NKB/15] (T/D)3 at low T

agrees with experiment
(metals have CV= AT + BT3 due to electrons)

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Phonon density of states in 3D

assume 3D modes are equally spaced in k

maxiumum crystal dimension Lx=N1/3a

continuous boundary conditions: kx=2/Lx, 4/Lx, ...
g(k)=(k)-1=V/(2)3
if k taken to be |k| then g()=4k2g(k)dk/d
g(k) = (Vk2/22)
need extra factor of 3 because L/T modes in 3D

density of modes g()=g(k)dk/d

assume = v0k
this is Debye approximation
g() = 3Vk2 / 22v0 = 3V2 / 22v03

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