Documentos de Académico
Documentos de Profesional
Documentos de Cultura
Lecture Notes
Abstract
These notes represent the material covered in the Part II lecture Statistical Physics.
They are largely based on the more extended lecture notes by David Tong [2]. The main
purpose of these notes to provide as close as possible a one-to-one representation of the
course as it appears on the black board in the lecture room. This comes, at times, at the
expanse of uniformly using complete sentences and instead using short phrases and the
like.
Readers interested in more details as well as a wider range of subjects, will find David
Tong’s lecture notes an excellent source and may also find the following books of interest.
• E. Mandl, “Statistical Physics” .
• L. D. Landau & E. M. Lifshitz, “Statistical Physics” .
• F. Reif, “Fundamentals of Statistical and Thermal Physics” .
• M. Kardar, “Statistical Physics of Particles”, “Statistical Physics of Fields”; see also
Kardar’s webpage [3].
• A. B. Pippard, “The Elements of Classical Thermodynamics” .
Example sheets for this course will be available on the web page
http://www.damtp.cam.ac.uk/user/examples
Ulrich Sperhake
1
CONTENTS 2
Contents
A The fundamentals of statistical physics 3
A.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
A.2 The microcanonical ensemble . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
A.2.1 Entropy and the 2nd law of thermodynamics . . . . . . . . . . . . . . . . 5
A.2.2 Temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
A.2.3 The Two-State system . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
A.2.4 Pressure, Volume, 1st law of thermodynamics . . . . . . . . . . . . . . . . 12
A.3 The canonical ensemble . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
A.3.1 The partition function . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
A.3.2 Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
A.3.3 Free energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
A.4 The grand canonical ensemble . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
A.4.1 The chemical potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
A.4.2 The grand canonical ensemble . . . . . . . . . . . . . . . . . . . . . . . . 21
A.4.3 The grand canonical potential . . . . . . . . . . . . . . . . . . . . . . . . 21
B Classical Gases 23
B.1 From QM to classical . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
B.2 Ideal gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
B.2.1 Equipartition of energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
B.2.2 Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
B.2.3 The ideal gas in the GrCE . . . . . . . . . . . . . . . . . . . . . . . . . . 27
B.3 Maxwell distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
B.4 Diatomic gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
B.5 Interacting gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
B.5.1 Mayer f function and B2 . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
B.5.2 Van der Waals equation of state . . . . . . . . . . . . . . . . . . . . . . . 34
C Quantum Gases 36
C.1 Density of states . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
C.1.1 Relativistic systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
C.2 Photons: Blackbody Radiation . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
C.2.1 Planck distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
C.2.2 Cosmic Microwave Background (CMB) . . . . . . . . . . . . . . . . . . . 40
C.2.3 The birth of QM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
C.3 Phonons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
C.4 The diatomic gas revisited . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
C.5 Bosons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
C.5.1 Bose-Einstein (BE) distribution . . . . . . . . . . . . . . . . . . . . . . . 44
C.5.2 QM gas at high T . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
C.5.3 Bose Einstein condensation . . . . . . . . . . . . . . . . . . . . . . . . . 47
A THE FUNDAMENTALS OF STATISTICAL PHYSICS 3
D Classical Thermodynamics 59
D.1 Temperature and the 0th law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
D.2 The 1st law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
D.3 The 2nd law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
D.3.1 The Carnot cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 62
D.3.2 Thermodynamic temperature scale and ideal gas . . . . . . . . . . . . . . 63
D.3.3 Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
D.4 Thermodynamic potentials: Free Energy, Enthalpy . . . . . . . . . . . . . . . . 67
D.4.1 Maxwell’s relations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
D.5 The 3rd law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
E Phase transitions 70
E.1 Liquid-gas transition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
E.1.1 Phase equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
E.1.2 The Clausius-Clapeyron Equation . . . . . . . . . . . . . . . . . . . . . . 72
E.1.3 The critical point . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
E.2 The Ising model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 75
E.2.1 Mean-field theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
E.2.2 Critical exponents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
E.3 Landau Theory . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
E.3.1 Second order phase transitions . . . . . . . . . . . . . . . . . . . . . . . . 81
E.3.2 First order phase transitions . . . . . . . . . . . . . . . . . . . . . . . . . 82
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We will see that this can be done quite rigorously for many laws: ideal gas law, Wien’s dis-
placement, . . .
Not all macrosystems are understood at micro level: black holes, high T super conductors
E, N, ...
Isolated system: no exchange of energy, particles with outside
world
P R
We do this QM, but applies to classical systems as well ( → )
our view: mixed state with probability p(n) for state |ni
X
expectation value hÔi = p(n)hn|Ô|ni
n
23 )
Comments: • Ω(E) is absurdly large! E.g. 1023 2-state particles ⇒ Ω(E) = 2(10
• In QM, energy levels are discrete. For N ∼ 1023 they are finely spaced
→ almost like continuum.
We implicitly define Ω(E) as the # of states with energy ∈ [E, E + ∆E);
∆E ≪ measurement accuracy, ≫ level spacing
X
⇒ Ω(Etot ) = Ω1 (Ẽ1i ) Ω2 (Etot − Ẽ1i )
{Ẽi }
" #
X S1 (Ẽ1i ) S2 (Etot − Ẽ1i )
= exp +
kB kB
{Ẽi }
⇒ Ω(Etot ) ≥ Ω(E1 , E2 )
⇒ ∆S ≥ 0
A.2.2 Temperature
Note: We are slightly departing here from the microcanonic assumption E = const.
This is to be viewed as an ensemble of systems with different E.
1 ∂S
Def.: Temperature T : =
T ∂E
∂S1 ∂S2
⇒ − = 0 ⇒ T1 = T2
∂E E1 ∂E E2
⇒ No energy transfer corresponds to equal T1 = T2 (before contact) as expected.
3) Let us assume small energy transfer: δE1 = −δE2
!
∂S1 ∂S2 ∂S1 ∂S2 1 1
⇒ δS ≈ δE1 + δE2 = − δE1 = − δE1
∂E E1 ∂E E2 ∂E E1 ∂E E2 T1 T2
Heat capacity
∂E
Def.: C ≡
∂T
• consider E a function of T
∂S ∂S ∂E C
⇒ = =
∂T ∂E ∂T T
∂S
⇒ C=T
∂T
δQ
we will see this as C = in thermodynamics
δT
where we also specify what’s kept constant: CV , CP , . . .
Z T2
C(T )
we can measure entropy differences: ∆S = dT
T1 T
C
Def.: specific heat capacity c =
N
∂S 1 ∂2S ∂ 1 ∂T ∂ 1 1
Note: = ⇒ 2
= = =− 2
∂E T ∂E ∂E T ∂E ∂T T T C
∂2S
Almost all substances have C > 0 ⇒ <0
∂E 2
⇒ The extremum in Eq. (∗) is really a max.
Stirling’s formula
We often have ln N!
1 1
Stirling: ln N! = N ln N − N + ln(2πN) + O (Examples)
2 N
ln p
N
X
For now: ln N! = ln p
p=1
Z N Z N
≈ ln p dp = 1 ln p dp
1 1 1 2 3
... p
Z N
p
= [p ln p]N
1 − dp = N ln N − (N − 1)
1 p
⇒ ln N! ≈ N ln N − N (lower limit!)
A THE FUNDAMENTALS OF STATISTICAL PHYSICS 10
Two-spin-state system
Let E↓ = 0, E↑ = ǫ
⇒ E = N↑ ǫ
what is Ω(E)?
N
N!
⇒ Ω(E) = N↑
=
N↑ ! (N − N↑ !)
N!
⇒ S(E) = kB ln = kB [ln N! − ln N↑ ! − ln(N − N↑ )!]
N↑ ! (N − N↑ )!
≈ kB [N ln N − N − N↑ ln N↑ + N↑ − (N − N↑ ) ln(N − N↑ ) + N − N↑ ]
= kB [(N − N↑ ) ln N + N↑ ln N − N↑ ln N↑ − (N − N↑ ) ln(N − N↑ )]
N − N↑ N↑ E
= −kB (N − N↑ ) ln + N↑ ln N↑ =
N N ǫ
E E E E
= −kB N 1− ln 1 − + ln
Nǫ Nǫ Nǫ Nǫ
S(E)
special cases: S(0) = 0
Nǫ
S = kB N ln 2 maximum
2
S(Nǫ) = 0
0 Nε / 2 Nε E
A THE FUNDAMENTALS OF STATISTICAL PHYSICS 11
1 ∂S kB Nǫ
Temperature: = = ... = ln −1
T ∂E ǫ E
N↑ E 1
⇒ = = ǫ/(k T )
N Nǫ e B +1
N↑ 1
For T → ∞: =
N 2
Nǫ
What happens for E > ?
2
T < 0 ⇒ as we increase E, Ω(E) decreases
1
view as going through 0 to negative values
T
∂E ∂ Nǫ Nǫ2 eǫ/(kB T ) C
Heat capacity: C = = =
∂T ∂T eǫ/(kB T ) +1 kB T 2 (eǫ/(kB T ) + 1)2
ǫ
• C max near T ∼
kB
• T → 0 ⇒ C ∼ e−ǫ/(kB T ) → 0
T
“gap to first excited state”
Schottky anomaly
⇒ C increases with T .
for special cases at low T : e.g. paramagnetic salts
⇒ S(E, V ) = kB ln Ω(E, V )
1 ∂S
= ; “keep V constant”
T ∂E V
1 ∂S
Recall: we defined = and concluded that
T ∂E
2 systems keep their energies E1 , E2 if they have same T
∂S
Def: “Pressure”: p≡T
∂V E
∂S ∂S 1 p
First Law: from our definitions: dS = dE + dV = dE + dV
∂E V ∂V E T T
⇒ dE = T dS − pdV
Note: pdV = p A dx = F dx
dx
= work done by system
p
A
sign: dV < 0
⇒ dE > 0
∂E ∂S
heat capacity: we now write CV = =T
∂T V ∂T V
↑
δQ
Strictly but it’s the same since dV = 0
δT V
∂S ∂E
analagously: Cp = T (don’t use here!)
∂T p ∂T
Ludwig Boltzmann: did a lot of this in the absence of proof for atoms!
• closed system S
S
• at equilibrium temperature T
ΩR = # of states of reservoir; SR = kB ln ΩR
R large ⇒ En ≪ Etot
X
X SR (Etot − En ) SR (Etot ) ∂SR En
⇒ Ω(Etot ) = exp ≈ exp −
k B k B ∂E k
n n | {ztot} B
1
=
T
X
⇒ Ω(Etot ) ≈ eSR (Etot )/kB e−En /(kB T )
n
e−En /(kB T )
⇒ probability that S is in state |ni: p(n) = X
e−Em /(kB T )
m
X
Def.: “partition function” Z≡ e−βEn
n
e−βEn
⇒ Boltzmann distribution: p(n) =
Z
Xh (1)
i Xh (2)
i
−βEm −βEn
= e e = Z1 Z2
m n
In QM we have 2 probabilities: - QM
Derivations from Z
X X En e−βEn
average energy: hEi = (pn En ) =
n n
Z
∂
⇒ hEi = − ln Z
∂β
energy fluctuations: ∆E 2 = (E − hEi)2 = hE 2 i − hEi2
∂2 ∂
⇒ ... ⇒ ∆E 2 = 2
ln Z = − hEi
∂β ∂β
∂hEi ∂β ∂hEi 1
heat capacity: CV = = = ∆E 2
∂T V ∂T ∂β kB T 2
⇒ ∆E 2 = kB T 2 CV
N
Y βǫ
⇒Z= Zk = 2N e−N βǫ/2 coshN
k=1
2
∂ Nǫ βǫ Nǫ sinh x ex − e−x
⇒ hEi = − ln Z = . . . = 1 − tanh = =
∂β 2 2 1 + eβǫ cosh x ex + e−x
CV = . . .
A.3.2 Entropy
MiCE: S = kB ln Ω(E) = kB ln of # states
⇒ Ωtot = ΩR ΩS
what is ΩS ?
W!
⇒ ΩS = Y = # of different ways to get p(1) W systems in state |1i,
[p(n)W ]!
n p(2) W systems into state |2i, etc.
⇒ Stot = kB (ln ΩR + ln ΩS ) we ignore SR
X
⇒ SS = kB ln ΩS = (Stirling)
. . . = −kB W p(n) ln p(n) = entropy of W systems
n
X
⇒ one system: S = −kB p(n) ln p(n) due to Gibbs
n
∂
⇒ S = kB (T ln Z)
∂T
A THE FUNDAMENTALS OF STATISTICAL PHYSICS 18
MiCE vs. CE
X
S = kB ln Ω(E) vs. S = −kB p(n) ln p(n)
n
⇒ Z ≈ Ω(E∗ )e−βE∗
1 ∂S ∂ ln Ω ∂ ln Ω
We’ll need: = = kB ⇒ β=
T ∂E ∂E ∂E
∂
⇒ hEi = − ln Z
∂β
∂
=− [ln Ω − βE∗ ]
∂β
∂E∗ ∂ ln Ω ∂E∗
=− + E∗ + β
∂β ∂E∗ ∂β
= E∗ (!)
∂ ∂ ∂ 2 ∂
entropy: S = kB (T ln Z) = kB [T (ln Ω − βE∗ )] ∂T = −kB β ∂β
∂T ∂T
∂
= kB ln Ω − kB βE∗ − kB T kB β 2 (ln Ω − βE∗ )
∂β
| {z }
=−E∗
= kB ln Ω(E∗ )
Maximizing entropy
∂ ∂ ∂ ∂
Recall E=− ln Z , S = kB (T ln Z) , = −kB T 2
∂β ∂T ∂β ∂T
∂ ∂
⇒ F = E − T S = kB T 2 ln Z − kB T ln Z − kB T 2 ln Z
∂T ∂T
⇒ F = −kB T ln Z
A THE FUNDAMENTALS OF STATISTICAL PHYSICS 20
⇒ S = S(E, V, N) = kB ln Ω(E, V, N)
1 ∂S ∂S
recall: = , p=T
T ∂E V,N ∂V E,N
∂S
Def.: chemical potential µ = −T
∂N V,E
1 p µ
1st law: dS = dE + dV − dN ⇒ dE = T dS − pdV + µdN
T T T
⇒ µ = “energy cost to add one particle”
⇒ fixed T and µ
e−β(En −µNn )
⇒ (Sec.
. . .3) ⇒ p(n) =
Z
X ∂
Entropy: S = −kB p(n) ln p(n) ⇒ . . . ⇒ S = kB (T ln Z)
n
∂T
∂
one also gets: hEi − µhNi = − ln Z
∂β
1 ∂
hNi = ln Z
β ∂µ
1 ∂2 1 ∂hNi
∆N 2 = 2 2
ln Z =
β ∂µ β ∂µ
View Φ = Φ(T, V, µ)
∂ ∂
with F = E − T S , Φ = E − T S − µN , = −kB T 2
∂β ∂T
∂ ∂
⇒Φ=− ln Z − T kB (T ln Z)
∂β ∂T
⇒ Φ = −kB T ln Z
A THE FUNDAMENTALS OF STATISTICAL PHYSICS 22
⇒ Φ must be ∼ V !
∂Φ
We know = −p ⇒ Φ = −p(T, µ) V
∂V T,µ
B Classical Gases
gas = particles flying around in a box
X X
⇒ Z1 = e−βEn = hn|e−β Ĥ |ni
n n
X Z Z
−β Ĥ
= hn| dq |qihq|e dq ′ |q ′ihq ′ |ni
n
Z ( )
X X
dq dq ′ hq|e−β Ĥ |q ′ i [hq ′ |nihn|qi] |nihn| = 1 , hq ′ |qi = δ(q − q ′ )
=
n
n
Z
⇒ Z1 = dqhq|e−β Ĥ |qi “ = Tr e−β Ĥ ”
B CLASSICAL GASES 24
1
Recall from QM: e eB̂ = eÂ+B̂+ 2 [Â,B̂]+...
Z 2
p̂
′ −βU (q) −β 2m ′ ′
= dq dp dp e hq|pihp|e |p ihp |qi
1 i
Note: hq|pi = hp|qi∗ = √ e ~ pq , hp|p′i = δ(p − p′ )
2π~
Z
1
In 3 dims.: Z1 = d3 q d3 pe−βH(~p,~q)
(2π~)3
s
2π~2
Def.: thermal de Broglie wavelength λ=
mkB T
V
⇒ Z1 =
λ3
Z1N VN
N indistinguishable particles: Z(N, V, T ) = = 3N
N! λ N!
exchange two particles → no new state! Hence N!
Recall: F = −kB T ln Z = −kB T [N ln V − 3N ln λ − ln N!]
∂F NkB T
p= − =+ ⇒ ideal gas law: pV = NkB T
∂V T V
p2 √ p
For one particle: hEi = ⇒ p∼ mE ∼ mkB T
2m
h
de Broglie wavelength λdB = ∼ λ up to factors of 2 or π
p
∂E 3
heat capacity: CV = = NkB
∂T V 2
Chemist Notation
1 mol ≡ NA atoms
B.2.2 Entropy
∂
Recall entropy for CE: S = kB (T ln Z)
∂T
s
∂ ∂ 2π~2 ∂ 1
ln λ = ln = ln T −1/2 = −
∂T ∂T mkB T ∂T 2T
∂
⇒ S = kB ln Z + kB T [N ln V − 3N ln λ − ln N!]
∂T
VN 3N
= kB ln 3N − ln N! + kB T Stirling : ln N! ≈ N ln N − N
λ 2T
VN 3
≈ kB ln 3N N + N + NkB
λ N 2
B CLASSICAL GASES 27
V 5
⇒ S = NkB ln 3 + “Sackur-Tetrode equation”
λN 2
" #
X X X
Zideal (µ, V, T ) = eβNn µ e−βEn = eβN µ e−βEm
n N m
տ
states for fixed N
∞ ∞
" N #
X βµN X N V 1
= e Zideal (N, V, T ) = eβµ
N =0 N =0
λ3 N!
eβµ V
= exp
λ3
1 ∂ eβµ V
⇒ hNi = N = ln Z =
β ∂µ λ3
3
λ N
⇒ µ = kB T ln
V
V
= average volume per particle
N
λ ≈ average de Broglie wavelength of particle
B CLASSICAL GASES 28
V
λ3 ≈ ⇒ QM effects important
N
V
classical limit ⇒ λ3 ≪ ⇒ µ<0
N
∂E
Comments: • µ= = energy cost of adding particle at constant S, V !
∂N S,V
⇒ E decreases ⇒ µ < 0
• µ > 0 possible for some special cases
1 ∂2
Fluctuations: ∆N 2 = ln Z = N
β 2 ∂µ2
∆N 1
⇒ =√ → 0 in thermodynamic limit
N N
eβµ V
Recall: pV = −Φ = kB T ln Z = kB T = kB T N ideal gas law !
λ3
mv 2
−
⇒ probability that atom speed in [v, v + dv]: p(v) = N v 2e 2kB T “Maxwell
3/2 distribution”
m
N = 4π
2πkB T
B CLASSICAL GASES 29
p(v)
Z ∞
3kB T
⇒ hv 2 i = p(v) v 2dv = . . . = Xe
0 m
equipartition of energy
ր
He
0 1000 2000
km / s
⇒ p(v) dvx dvy dvz = φ(vx ) φ(vy ) φ(vz ) dvx dvy dvz
2
It can be shown that the only solution is φ(vx ) = Ae−Bvx
2
⇒ p(v) dvx dvy dvz = 4πv 2 p(v)dv = 4πA3 v 2 e−Bv dv
m
equipartition of energy ⇒ B =
2kB T
ii) vibration
i) Rotation
1
Lagrangian: Lrot = I θ̇2 + sin2 θ φ̇2
2
∂Lrot ∂Lrot
⇒ conjugate momenta: pθ = = I θ̇ , pφ = = I sin2 θ φ̇
∂ θ̇ ∂ φ̇
p2θ p2φ
⇒ Hamiltonian: Hrot = pθ θ̇ + pφ φ̇ − Lrot = +
2I 2I sin2 θ
Z Z r
1 −βHrot
−ax2 π
⇒ Zrot = 2
e dpθ dpφ dθ dφ e dx =
(2π~) a
Z π Z 2π
2πI 2I
= sin θ dθ dφ =
β(2π~)2 0 0 β~2
∂ ∂ 1
⇒ Erot = − ln Zrot = − [− ln β ± . . .] = = kB T
∂β ∂β β
B CLASSICAL GASES 31
ii) vibration
ζ
harmonic oscillator with frequency ω
p2ζ 1
⇒ Hvib = + mω 2 ζ 2
2m 2
Z
1
⇒ Zvib = e−βHvib dpζ dζ
2π~
Z p2
1 ζ mω 2 ζ 2 1 kB T
= e−β 2m e−β 2 dpζ dζ = =
2π~ ~βω ~ω
CV
7
diatomic gas: CV = NkB 7/2
vib
2
5/2
rot
Note: • I, ω dropped out
3/2
• at lower T : dof’s frozen out, e.g. H2 : tran
100 1000
QM effect; visible in hot gas! T/K
goal: get Bi (T ) from first principals, i.e. potential U(r) between atoms
1 p1 p2
2 features of U(r): • attractive 6
: dipols p1 , p2 ⇒ pot. energy 3
r r
p1
instantaneous dipol p1 ⇒ electr. field E ∼
r3
p1
⇒ induced dipol p2 ∼ E ∼
r3
“van der Waals interaction”
r 12 r 6
0 0
Lennard-Jones potential: U(r) ∼ − ; 12 = 6 · 2 chosen for convenience
r r
U
∞ r < r0
hard-core potential: U(r) =
r0 6
−U0 r
r ≥ r0
N
X p~2i X
H= + U(rij ) ; rij ≡ |~ri − ~rj |
i=1
2m i>j
տ
count pairs once!
N
Z Y
1 1
⇒ Z(N, V, T ) = d3 pi d3 ri e−βH
N! (2π~)3N i=1
"Z # "Z #
1 1 Y P 2 Y P
= 3N
d3 pi e−β j p~j /(2m) · d3 ri e−β j<k U (rjk )
N! (2π~) i i
Z Y
1 P
= 3N d3 ri e−β j<k U (rjk )
λ N!
| i {z }
hard!
B CLASSICAL GASES 33
P X β2 X
1st try: Taylor: e−β j<k U (rjk )
= 1−β U(rjk ) + U(rjk ) U(rlm ) ± . . .
j<k
2 j<k, l<m, l>j
r → ∞ ⇒ f (r) → 0 , r → 0 ⇒ f (r) → −1
P Y
Def.: fij ≡ f (rij ) ⇒ e−β j<k U (rjk )
= (1 + fjk )
j<k
Z Y !
1 X X
⇒ Z(N, V, T ) = d 3 ri 1 + fjk + fjk flm + . . .
N! λ3N i j>k j>k, l>m, l>j
1 N2
We have N(N − 1) ≈ terms of type I12
2 2
Z
VN N2 3
(1 + ǫ)N ≈ 1 + Nǫ
⇒ Z(N, V, T ) = 1+ d r f (r) + . . .
N! λ3N 2V
Z N
N 3
≈ Zideal 1 + d r f (r)
2V
Z
N 3
⇒ F = −kB T ln Z = Fideal − NkB T ln 1 + d r f (r)
2V
| {z }
→B2 (T )
B CLASSICAL GASES 34
Cases:
6
r 6
0
high T limit: βU0 ≪ 1 ⇒ eβU0 (r0 /r) ≈ 1 + βU0
r
Z Z r0 Z ∞
3 4πU0 r06
⇒ f (r)d r ≈ −4π r 2 dr + dr
0 kB T r0 r4
3
4πr0 U0
= −1
3 kB T
B CLASSICAL GASES 35
pV N a 2πr03U0 2πr03
⇒ =1− −b ; a= , b=
NkB T V kB T 3 3
−1
V N2 N N2 V
⇒ . . . ⇒ kB T = p+ 2a 1+ b ≈ p+ 2a −b
N V V V N
N
“van der Waals EOS”: valid at low , high T
V
NkB T N2
⇒p= −a 2
V − bN V
etc.
N −1
Y N2 Ω
(V −mΩ) ≈ V N
whole configuration space: 1− + ... Ω≪V
m=0
2 V
N
Ω
≈ V −N = (V − Nb)N
2
• Our method can only handle potentials
1
U(r) ∼ with n > 3 . Otherwise divergent integral of f (r)
rn
a
• 2nd virial term of van der Waals EOS: B2 (T ) = − −b
kB T
• Higher-order virial coefficients: e.g. cluster expansion,
C Quantum Gases
gases where QM effects are important; includes light, phonons,. . .
X
one particle: Z1 = e−βE~n
~
n
s
2π~2 E~n ~2~k 2 λ2~n2
recall λ = ⇒ exponent =β ∼ 2
mkB T kB T 2m L
~2 k 2 ~2 k
E= ⇒ dE = dk
2m m
Z r Z
X V 2mE m
⇒ ≈ 2 dE =: g(E)dE ,
2π ~2 ~2
~
n
3/2
V 2m √
g(E) = 2 E
4π ~2
C QUANTUM GASES 37
2πc
Photons: wavelength λ , frequency ω = = kc
λ
energy E = ~ω ; m=0
V~ ω3
⇒ E(ω) = = photon energy density in frequency space
π 2 c3 eβ~ω − 1
Comments: • as T decreases:
• ωmax = ζ kB~T ,
→ color of object at T
C QUANTUM GASES 39
Z ∞
V (kB T )4 x3
total energy: E= 2 3 dx x = β~ω
π c ~3 ex − 1
|0 {z }
4
= ... = π15
E π 2 kB
4
⇒ = T4
V 15~3 c3
E c π 2 kB
4
J
energy flux from object = luminosity: L= = σT 4 ; σ= = 5.67 × 10 −8
V 4 60~3 c2 m2 s K
“Stefan-Boltzmann law” (cf. Reif [1] for details)
Z ∞
V kB T 2 −β~ω
pressure: F = −kB T ln Z = 2 3 ω ln 1 − e dω int. by parts
π c 0
Z ∞
V~ ω 3 e−β~ω
=− 2 3 dω
3π c 0 1 − e−β~ω
Z ∞
V~ 1 x3 V π2
=− 2 3 4 4 x
= − 3 3
(kB T )4
3π c β ~ 0 e −1 45~ c
∂F 1E 4σ 4
⇒ p= − = = T
∂V T 3V 3 c
1
Note: photon pressure = photon energy; important in cosmology!
3
∂F 16V σ 3 ∂E 16V σ 3
We also get: S=− = T , CV = = T
∂T V 3c ∂T V c
C QUANTUM GASES 40
Z ∞
Problem: ERJ (ω) dω diverges: “ultraviolet catastrophe”
0
C.3 Phonons
vibrations of crystal = sound waves
L
differences from photons: • cs instead of c
⇒ 3N ways of moving
Z ωD
set 3N = g̃(ω) dω which is the number of states available for one phonon
0
Z ωD 1/3
3 V ω2 V ωD 3
6π 2 N
⇒ 3N = dω = ⇒ ωD = cs
0 2 π 2 c3s 2π 2 c3s V
~ωD
Def.: Debye temperature TD = = temperature at which highest-frequency
kB
states become excited
TD ≈ 100 K for lead, 2 000 K for diamond, ≈ 200 . . . 400 K for many materials
C QUANTUM GASES 42
no analytic solution
Z ∞
x3 π4
Limits: 1) T ≪ TD ⇒ upper int. limit ≈ ∞: dx =
0 ex − 1 15
3
∂E 2π 2 V kB
4
3 12π 4 T
⇒ CV = = T = NkB
∂T V 5(~cs )3 5 TD
“Dulong-Petit law”
5/2
rot
1) Rotation
3/2
tran
p2θ p2φ
H= + 100 1000
2I 2I sin2 θ T/K
~2
QM ⇒ E levels: E= j(j + 1) ; j = 0, 1, 2, . . .
2I
degeneracy 2j + 1 (Lz quantum numbers)
∞
X 2 j(j+1)/(2I)
⇒ Zrot = (2j + 1)e−β~
j=0
~2 β~2
a) T ≫ ⇒ ≪1
2IkB 2I
Z ∞
2 x(x+1)/(2I) 2I
⇒ Zrot ≈ (2x + 1)e−β~ dx = = Zclassic
0 β~2
~2
b) T ≪ ⇒ Zrot ≈ 1
2IkB
T insufficient to excite even the 1st state above ground level.
2) Vibration
1
harmonic oscillator: En = ~ω n +
2
X X e−β~ω/2 1
e−β~ω(n+ 2 ) = e−β~ω/2
1
⇒ Zvib = e−β~nω = =
n n
1−e −β~ω
2 sinh β~ω
2
C QUANTUM GASES 44
~ω 1
a) T ≫ ⇒ Zvib ≈ = Zclass
kB β~ω
~ω
b) T ≪ ⇒ Zvib ≈ e−β~ω/2 = contribution from zero-point energy
kB
∂ ~ω
⇒ energy offset Evib = − ln Zvib = , but no contribution to CV
∂β 2
C.5 Bosons
QM: 2 types of particles: 1) bosons: integer spin: ψ(~r1 , ~r2 ) = ψ(~r2 , ~r1 )
1
2) fermions: 2
-integer spin: ψ(~r1 , ~r2 ) = −ψ(~r2 , ~r1 )
particles indistinguishable
⇒ system described by n1 ≡ # of particles in state |1i, n2 , n3 , . . .
X P X
CE: Z = e−β r nr Er ; sum over all states {nr } with nr = N ; Tricky!
{nr } r
C QUANTUM GASES 45
X X
“ # particles in state” = “ states of particles”
states particles
1 ∂ X 1 X 1
⇒ N= ln Z = β(Er −µ) − 1
=: hnr i ; hnr i =
β ∂µ r
e r
eβ(Er −µ) −1
BE distribution
TD limit ⇒ nr ≈ hnr i
Ideal BE gas
~2 k 2
1 particle: E =
2m
3/2
V 2m √
Recall: # of states in [E, E + de) for one particle: g(E)dE = 2 E dE
4π ~2
Z Z
X g(E)
→ N= hnr i = g(E) hnr i dE = dE = N(µ, T )
r
ζ −1eβE
−1
Comment: in practice N often fixed, e.g. # of He4 ; GrCE chosen for convenience!
Φ
pressure: p=−
V
1 1X
⇒ pV = ln Z = − ln 1 − ζe−βEr
β β r
Z
1
=− g(E) ln 1 − ζe−βE dE
β | {z } | {z }
u′ v
Z ∞ 3/2 Z ∞
E 1 E g(E) 1 2m E 3/2
x = βE, ζ ≪ 1
= dE = dE
V V 0 ζ −1eβE − 1 4π 2 ~2 0 ζ −1eβE − 1
3/2 Z ∞
1 2m ζ 3/2 −x −x
= 2 x e 1 + ζe + . . . dx
4π ~2 β 5/2 0
3ζ ζ
= ... = 3 1 + √ + ... (∗∗)
2λ β 4 2
∞ Z ∞ Z
1 X m n−1 −mx 1 X zm
= z x e dx = un−1e−u du u = mx
Γ(n) m=1 Γ(n) m=1 mn
| {z }
=Γ(n)
C QUANTUM GASES 48
∞
X zm
⇒ gn (z) = monotonically increasing with z
m=1
mn
∞
X 1
Def.: Zeta function ζ̂(s) ≡
n=1
ns
3
⇒ gn (1) = ζ̂(n) ; g3/2 = ζ̂ ≈ 2.612
2
3/2 Z ∞
N 1 2m x1/2 1
Recall: = 2 dx = g3/2 (ζ) (∗)
V 4π ~2 β 0 ζ −1 ex − 1 λ3
N
For fixed : decrease T ⇒ λ increases ⇒ g3/2 (ζ) must increase ⇒ ζ increases
V
What’s wrong?
3/2 Z
X V 2m √
Answer: we used ≈ 2 E dE
k
4π ~2
R P
The ground state E = 0 doesn’t contribute to but should be in
T < Tc ⇒ ζ close to 1
V
⇒ N≈ g3/2 (1) + hn0 i
λ3
3 3/2
n0 V λc T
⇒ =1− g3/2 (1) = 1 − =1−
N Nλ3 λ Tc
⇒ at T < Tc a macroscopic number of particles is in the ground state
“BE condensation”
Z
2 2 E g(E) kB T V
EOS: Recall pV = Etot = dE = g5/2 (ζ)
3 3 ζ −1 eβE − 1 λ3
Comment: The ground-state contribution can be shown to be negligible
kB T
T < Tc ⇒ ζ ≈ 1 ⇒ p = g5/2 (1)
λ3
N
Note: p ∼ T 5/2 and p independent of particle density
V
Case 1: T < Tc
dζ 15 V kB
ζ≈1 ⇒ ≈ 0 and CV ≈ g5/2 (1)
dT 4 λ3
Case 2: T & Tc
∞
X ζm dgn 1
gn (ζ) = ⇒ = gn−1 (ζ)
m=1
mn dζ ζ
dg5/2 dg5/2
⇒ = ζ −1 g3/2 (ζ) ; as T → Tc : → g3/2 (1)
dζ dζ
dζ
We still need
dT
Nλ3
For T > Tc , (∗) is still valid: = g3/2 (ζ)
V
n0
−6 6
say ζ = 1 − 10 ⇒ n0 ≈ 10 ⇒ ζ ≈ 1 ∧ ≈0
N
Z ∞
dg3/2 1 1 1 x−1/2
= g1/2 = dx diverges for ζ → 1
dζ ζ ζ Γ(1/2) 0 ζ −1ex − 1
Z ǫ
1 1 x−1/2 x
e ≈1+x
= −1
dx + finite
ζ Γ(1/2) 0 ζ (1 + x) − 1
Z ǫ r
1 x−1/2 x
= dx + . . . u=
Γ(1/2) 0 (1 − ζ) + x 1−ζ
Z ǫ
2 1 1
=√ du + . . .
1 − ζ Γ(1/2) 0 1 + u2
p
⇒ Series expansion: g3/2 (ζ) = g3/2 (1) + A 1 − ζ + . . .
Nλ3 p
⇒ = g3/2 (ζ) ≈ g3/2 (1) + A 1 − ζ
V
2
1 Nλ3
⇒ ζ ≈ 1 − 2 g3/2 (1) −
A V
2/3 3/2
2π~2 1 N Tc λ3 N 1
Recall: Tc = ⇒ =
kB m g3/2 (1) V T V g3/2 (1)
C QUANTUM GASES 51
" 3/2 #2 2
[g3/2 (1)]2 Tc T − Tc
⇒ ζ ≈1− 1− ≈1−B T = Tc (1 + ǫ)
A2 T Tc
15 kB V dζ
So for T & Tc : CV = 3
g5/2 (ζ) + b̃ ; b̃ finite > 0
4 λ dT
15 kB V T − Tc
⇒ CV = 3
g5/2 (ζ) − b with b > 0
4 λ Tc
Comments: • The first term smoothly goes over to the result of Case 1) for T < Tc
only in TD limit
Tc T
Superfluid Helium-4
He4 : bosons
“λ transition”
C.6 Fermions
non-interacting fermions: e− , in metals, He3 , white dwarfs, neutron stars, . . .
fermions: integer + 21 spin, ψ(~r1 , ~r2 ) = −ψ(~r2 , ~r1 ) ⇒ Pauli exclusion
X
GrCE: Zr = e−βn(Er −µ) = 1 + e−β(Er −µ) : state occupied or not
n=0,1
Y
Z= Zr
r
1 ∂ X 1 X
⇒ N = hNi = ln Z = = hnr i
β ∂µ r
eβ(Er −µ) + 1 r
1
⇒ hnr i = “Fermi-dirac” (FD) disttibution
eβ(Er −µ) +1
µ can be positive or negative; unlike BE!
Z
1 1 2
pV = −Φ = ln Z = g(E) ln 1 + ζe−βE dE = Etot int by parts
β β 3
λ3 N
high T ⇒ Sec.
. . .5.2 ⇒ pv = NkB T 1+ √ +...
4 2g V
| {z s }
=B2 (T )
EF
Def.: Fermi temperature TF ≡
kB
∼ 104 K for e− in metal ; ∼ 107 K in white dwarfs
p
Momentum space: ~kF = 2mEF kz
ky
All states with |~k| ≤ kF filled
What is EF (N) ?
Z ∞ Z EF 3/2
g(E) gs V 2m 3/2
T →0 ⇒ N = −1 βE
dE = g(E)dE = 2 2
EF
0 ζ e +1 0 6π ~
2/3
~2 6π 2 N
⇒ EF =
2m gs V
Z EF
3
⇒ E = hEi = E g(E) dE = NEF
0 5
2
⇒ pV = NEF “degeneracy pressure” 6= 0 even at T = 0
5
important for compact stars
C QUANTUM GASES 54
EF E
dN dµ
Claim: = 0 at T = 0 if = 0 at T = 0.
dT dT
Z ∞ Z ∞
dN d g(E) d 1
Proof: = dE = g(E) dE
dT dT 0 eβ(E−µ) + 1 0 dT eβ(E−µ) + 1
Z ∞
∂ 1
≈ g(EF ) dE
0 ∂T eβ(E−µ) + 1
↑ տ
d
1) dT
(FD) ≈ 0 2) no inner deriv. of µ ;
except E ≈ EF µ = EF
Z ∞
dN E − EF 1
⇒ ≈ g(EF ) 2 2 dE ≈ 0
dT 0 kB T 4 cosh [β(E − EF )/2]
| {z } | {z }
odd in E−EF even in E−EF
Z ∞
∂E ∂ 1
Heat capacity: CV = = E g(E) dE
∂T N,V 0 ∂T eβ(E−µ) + 1
3
Taylor: E g(E) ∼ E 3/2 ⇒ E g(E) ≈ EF g(EF ) + g(EF ) (E − EF )
2
Z ∞
3 ∂ 1
⇒ CV = EF g(EF ) + g(EF ) (E − EF )
0 | {z } |2 {z } ∂T eβ(E−EF ) + 1
even | {z }
odd
odd in (E − EF )
cf. above
C QUANTUM GASES 55
Z ∞
3 x2
⇒ . . . ⇒ CV ≈ g(EF ) T 2 x dx
x = β(E − EF )
2 −∞ 4 cosh 2
Z ∞ Z ∞
Here we extended the integral from . . . dx to . . . dx because
−βEF −∞
⇒ CV ∼ T g(EF )
⇒ CV ∼ g(EF ) T
3/2
Recall: N ∼ EF ∼ EF g(EF ) ∼ TF g(EF )
T
⇒ CV ∼ NkB
TF
Comment: More rigorous treatment: Sommerfeld expansion ; cf. Sec. 3.6.4 in D. Tong [2]
π2 T
Lengthier calculation ⇒ CV = NkB
2 TF
⇒ CV = γT +αT 3
TD3
One can show that the 2 contributions are ≈ equal for T 2 ∼
50 TF
TD3
Typically: TD ∼ 102 K , TF ∼ 104 K ⇒ = O(1) K
50 TF
When stars exhaust their fuel (H, He, . . . ): T → 0 , degeneracy pressure ; “White Dwarfs”
3 GM 2
constant density approximation ⇒ Egrav =− ; G = Newton’s constant
5 R
minimize Egrav + Ekin ⇒ . . . ⇒ R ∼ M −1/3 (example sheet)
1
Case 1: leading term > 0
R
dEtot 1
⇒ = 0 has a solution: term balances R term
dR R
⇒ star settles into new equilibrium
1
Case 2: leading term r < 0 ⇒ no equilibrium ⇒ neutron star or black hole
R
3/2
~c 1
This happens if M > Mc ∼ ≈ 1.5 M⊙
G m2p
C QUANTUM GASES 57
⇒ 2 effects: ~
1) Coupling of spin to B
~
2) Lorentz force ~v × B
Here 1)
∂E
Def.: Magnetization M ≡
∂B
one e− : Espin = s µB B
µB V
⇒ M = µB (N↑ − N↓ ) = 3
f3/2 ζeβµB B − f3/2 ζe−βµB B
λ
2µB V ζ
⇒ M≈ sinh (βµB B)
λ3
2V ζ
likewise: N ≡ N↑ + N↓ ≈ cosh (βµB B)
λ3
⇒ M ≈ µB N tanh (βµB B) = classical result!
C QUANTUM GASES 58
∂M
Def.: magnetic susceptibility χ =
∂B
For small B : tanh (βµB B) ≈ βµB B
Nµ2B
⇒ χ(B = 0) = “Curie’s law”
kB T
(ln ζ)n
Low T limit: One can show for βµ ≫ 1: fn (ζ) =
Γ(n + 1)
3/2
µB V 2m 3/2 3/2
⇒ M = µB (N↑ − N↓ ) = (E F + µ B B) − (EF − µ B B)
6π 2 ~2
3/2
µ2B V 2m 1/2
µB B ≪ EF ⇒ M ≈ 2 2
EF B
2π ~
3/2
gs V 2m √
density of states: g(E) = E ; gs = 2
4π 2 ~2
⇒ M ≈ µ2B g(EF )B
∂M
⇒ χ= = µ2B g(EF ) ∼ const
∂B
Interpretation: The e− deep below the Fermi surface cannot flip their spin because those
states are already occupied. Only e− at the Fermi surface can flip the state.
These e− have density of states g(EF ).
µ2B !
Effect 2) [Lorentz force] ⇒ . . . ⇒ M = − g(EF )B < 0 ; “diamagnetism”; cf. [2].
3
D CLASSICAL THERMODYNAMICS 59
D Classical Thermodynamics
Macroscopic description of systems without regard to microscopic constituents
⇒ ∆E = Q + W
we write dE = dQ
¯ + dW
¯
meaning of d¯: There exists no function W (p, V ) such that “dW = −pdV ”
V
D CLASSICAL THERMODYNAMICS 61
Def.: Reversible process ≡ quasi-static process that can be run backwards: “no friction”
I
For a roundtrip: dE = 0 p
p2
I
But in general: p dV 6= 0
I I
st
1 law ⇒ dQ
¯ = p dV p
1
V1 V2 V
It would be great to run this circle such that heat is transformed into work...
2nd law: Kelvin: No process is possible whose sole effect is to extract heat from
Keywords: “sole effect”! E.g. fridge uses work to cool a colder system.
W QC
Def.: efficiency η ≡ =1−
QH QH
Kelvin forbids η = 1 ⇔ QC = 0
Clausius ⇒ Q′H ≥ QH
Q′C Q′H − Q′C QH − QC QH − QC
⇒ ηIvor =1− ′ = ′
= ′
≤ = ηCarnot
QH QH QH QH
Suppose Ivor were reversible. Then likewise we’d show ηIvor ≥ ηCarnot
⇒ A reversible Ivor has the same η as Carnot. The only variables are TH , TC
⇒ η = η(TH , TC )
T2
Def.: Thermodynamic temperature: Choose T such that η = 1 −
T1
D CLASSICAL THERMODYNAMICS 64
pV
ideal gas: T =
kB T
3
energy E = NkB T
2
! 3
B → C : adiabatic expansion: dQ
¯ = 0 ⇒ dE = −pdV = NkB dT
2
NkB T 3 dV 3 dT
pV = NkB T ⇒ − dV = NkB dT ⇒ − =
V 2 V 2 T
3 p
⇒ − ln V = ln T + const ⇒ p ∼ V −5/3 AX
2
⇒ T V 2/3 = const
X B
2/3
2/3 2/3 TC VB
⇒ TH VB = TC VC ⇒ = 2/3
TH VC X
D X C
V
VD VC
C → D : isothermal compression: QC = −NkB TC ln = NkB TC ln
VC VD
Note: QC > 0 ; heat given away by engine
2/3 2/3
2/3 2/3 TC V ! V
D → A : adiabatic compression: TC VD = TH VA ⇒ = A2/3 = B2/3
TH VD VC
QC TC ln(VC /VD ) TC
Balance: η = 1 − =1− =1−
QH TH ln(VB /VA ) TH
D.3.3 Entropy
Notation: Count Q as heat absorbed by the system
Set T1 ≡ TH , T2 ≡ TC ⇒ Q1 = QH , Q2 = −QC
2
QC TC X Qi
Carnot cycle ⇒ = ⇒ for any Carnot cycle =0
QH TH i=1
Ti
p
Subdivide Carnot cycle: X A
QAB QCD
Normal cycle ABCD: ⇒ + =0
TH TC
E
X
QGF QEB
Mini cycle EBGF : ⇒ + =0 B
TF G TH X
FX
Bizarre cycle AEF GCD: ⇒ QAB = QAE + QEB X X
G
D C
X
QF G = −QGF V
QAE QF G QCD QAB − QEB QGF QCD
⇒ + + = − + =0
TH TF G TC TH TF G TC
dQ
¯
Comment: dS = ⇒ 1st law dE = T dS − p dV
T
⇒ This entropy is the same as that defined in Sec. A
Irreversibility
Z A II
dQ
¯ dQ
¯
⇒ ≤ S(B) − S(A) ; ≤ dS for irrev. process
I T T
V
Suppose, path I is adiabatic ⇒ dQ
¯ = 0 ⇒ S(B) ≥ S(A)
Isolated systems can only evolve to equal or higher entropy → time arrow
D CLASSICAL THERMODYNAMICS 67
Free energy
good if T = const
Vtot = VR + VS = const
ES + p VS − T SS
= SR −
T
Stot max if Gibbs free energy G = E + pV − T S = F + pV is min.
dG = −SdT + V dp
Enthalphy
Def.: Enthalpy H ≡ E + pV ⇒ dH = T dS + V dp
∂2E ∂2E
Second derivatives commute ⇒ =
∂S ∂V ∂V ∂S
∂p ∂T
⇒ − = “Maxwell Relations”
∂S V ∂V S
S
can be relaxed to: → 0 for T → 0 , N → ∞
N
⇒ the ground state entropy must not grow too much with N
Z
CV
Comment: In Sec. A.2.2, we saw: ∆S = dT
T
integral must converge ⇒ CV ∼ T n with n > 0
3
ideal gas: CV = NkB ∼ T 0 violates 3rd law
2
⇒ The 3rd law tells us that the low T world is QM, not classical
E PHASE TRANSITIONS 70
E Phase transitions
Abrupt, discontinuous changes in systems; cf. BE condensate
p
At T < TC : for some pressures: > 1 volume possible
dp
VB : > 0 ⇒ unstable
dv T
A B C
expand system → p increases X X X
VC : v ≫ b : gas
Maxwell construction
Clearly, between A, B, p(v) does not behave like van der Waals
At A) µ = µliq
At C) µ = µgas
We now assume that µliq = µgas and from A to C, µ does not change.
Z C Z B Z C
!
⇒ V dp = V dp + V dp = 0
A A B
⇒ The coexistence isotherm between A and C is p = const = pliq such that AAB = ABC
→ phase transition TC T
Def.: For an nth order phase transition, the nth deriv. of the thermodynamic potential
(typically F or G) is discontinuous.
∂G ∂F
Here: V = , S=− discontinuous
∂p ∂T
⇒ liquid-gas phase transition is 1st order.
As T → TC : Vliq → Vgas .
liquid
gas
TC T
E PHASE TRANSITIONS 73
T < TC ⇒ 3 roots
T > TC ⇒ 1 root
⇒ pC (v − vC )3 = 0
8a a
Compare coeffs. ⇒ kB TC = , vC = 3b , pC =
27b 27b2
The law of corresponding states
vC 27 (kB TC )2
Invert the last relations: b = ; a=
3 64 pC
T v p
Def.: reduced variables: T̄ ≡ , v̄ ≡ , p̄ ≡
TC vC pC
8 T̄ 3
⇒ vdW: p̄ = 1 −
3 v̄ − 3
v̄ 2
⇒ eliminate a, b
pC vC 3
⇒ compressibility ratio = should hold for all gases
kB TC 8
pC vC
Experiment: = 0.28 . . . 0.3 . OK, given that vdW is not really good for liquids.
kB TC
Critical exponents
8 T̄ 3 8T̄ 3 8T̄ 3
vdW: p̄ = 1 − 2
= − 2 = − 2
3 v̄ − 3
v̄ 3v̄liq − 1 v̄liq 3v̄gas − 1 v̄gas
1 ∂v
3) How does the compressibility κ ≡ − change as T → TC from T > TC ?
v ∂p T
∂p
At the critical point: =0
∂v TC
∂p
Taylor expand in T − TC ⇒ = −α(T − TC ) + . . . α = const
∂v T,v=vC
1
⇒κ∼
T − TC
How do these agree with experiment? How good is our vdW based model?
E PHASE TRANSITIONS 75
p − pC ∼ (v − vC ) ≈4.8
1
κ∼
(T − TC ) ≈1.2
The exponents are called “critical exponents”
Conclusion: The vdW EOS does a good job qualitatively, but is quantitatively inaccurate.
∆N 2 1
One can show that for T → TC : ∼κ∼ , i.e. diverges.
N T − TC
We work with averaged quantities! Becomes inaccurate for large fluctuations
spin down: ↓, si = −1
N
X
magn. field B ⇒ EB = −B si ; ↑ has lower energy ⇒ ↑ is “favored”
i=1
In contrast to our 2-state spin system from Sec. A.2.3, we use here interaction:
X
EI ≡ −J si sj
hiji
1 X 1 ∂
Def.: magnetization: m ≡ hsi i = ln Z
N i Nβ ∂B
E PHASE TRANSITIONS 76
⇒ si sj = [(si − m) + m] [(sj − m) + m]
Mean field theory: Fluctuations in the particle spin are small when summed over hiji .
1 X
= JNq m2 − (Jqm +B) si
|2 {z } |{z}
(2) i
(1)
(1) Each particle has q nearest neighbours: Nq pairs, but every one is counted twice!
X Nq
⇒ The sum has pairs – try for small N . . .
2
hiji
Nq
(2) Again, we have pairs in the sum.
2
Particles i and j appear equally in the sum si + sj
1
⇒ one sum over i and the factor 2
cancels the factor 2 from the sum si + sj .
1
Comments: • The JNqm2 term in E is merely a constant factor in Z
2
⇒ no effect on physics
!N
X X X
− 21 βJN qm2
P
Z=e ... eβBeff i si = eβBeff si
s1 sN si =±1
1 2 N 1 2
⇒ Z = e− 2 βJN qm e−βBeff + eβBeff = e− 2 βJN qm 2N coshN βBeff
E PHASE TRANSITIONS 77
1 ∂
⇒m= ln Z = tanh(βB + βJqm) ; implicit equation for m
Nβ ∂B
1) B = 0: ⇒ m = tanh(βJqm)
1
tanh x ≈ x − x3 ⇒ slope of tanh(βJqm) at m = 0: βJq
3 m
a) βJq < 1 ⇒ only one solution: m = 0
tanh
at high T (small β), temperature randomizes
m
the system ⇒ no average magnetization
⇒ m0 = ±1
Summary m B=0
+1
B = 0: • phase transition at T = TC
-1
Ising: Fix T < TC , vary B from positive to negative (or vice versa)
1) m at B = 0 as T → TC
1
Recall: m = tanh(βB + βJqm) = tanh(βJqm) ; tanh x ≈ x − x3
3
T = TC ⇒ βJq = 1
T . TC ⇒ βJq = 1 + ǫ
(1 + ǫ)3 3 1 + 3ǫ 3
⇒ m = tanh [(1 + ǫ)m] ≈ (1 + ǫ)m − m ≈ (1 + ǫ)m − m
3 3
1 + 3ǫ 2 1 √
⇒1≈1+ǫ− m ⇒ + ǫ m2 ≈ ǫ ⇒ m ≈ ± 3ǫ
3 3
Jq Jq Jq 1 Jq
ǫ= − = (TC − T ) ≈ (TC − T )
kB T kB TC kB T TC kB T 2
⇒ m ∼ ±(TC − T )1/2
dm
⇒ ∼ (TC − T )−1/2 → ∞ at TC
dT
cf. vgas − vliq ∼ (TC − T )1/2
∂m
3) Def.: magnetic susceptibility χ ≡ N ; cf. gas compressibility
∂B T
Fix B = 0; how does χ change as T → TC from T & TC ?
Nβ Jq
m = tanh (βB + β Jqm) ⇒ χ = 1+ χ at B = 0
cosh2 (β Jqm) N
1 1
d = 2: m0 ∼ (TC − T )α : αan = αmf =
8 2
m ∼ B 1/δ : δan = 15 δmf = 3
7
χ ∼ (T − TC )−γ : γan = γmf = 1
4
d = 3: Numerics ⇒ α ≈ 0.32 , δ ≈ 0.48 , γ ≈ 1.2
Same as van der Waals! Both are wrong in the same way.
1 1 N
e.g.: Ising model: F = − ln Z = JNqm2 − ln (2 cosh βBeff )
β 2 β
Note: F is a function of m
m 6= 0 ⇒ order ; m = 0 ⇒ randomness
-m0 m0
Ising model: a(T ) > 0 ⇔ T > TC ⇒ 1 equilibrium: m = 0 m
a(T ) < 0 ⇔ T < TC ⇒ 2 equilibria: m = ±m0
E PHASE TRANSITIONS 82
Comments: Landau theory predicts m0 ∼ (TC − T )1/2 for all dims. d of the Ising model
m
REFERENCES 83
References
[1] F. Reif. Fundamentals of statistical and thermal physics. McGraw-Hill, Inc., 1967.
[2] David Tong’s lecture notes on Statistical Physics:
http://www.damtp.cam.ac.uk/user/dt281/statphys.html.
[3] Mehran Kardar’s Lecture Notes:
http://web.mit.edu/kardar/www/teaching/.