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Ross McKenzie February 5, 2002

2

Introduction

These notes were prepared by Joel Gilmore, Mark Dowling, Jenny Riesz, Elizabeth Thomsen and Rohan Dalton, based on Ross McKenzie’s handwritten notes for PHYS2050 in 2001.

Very Important

These notes are not complete, and are not a substitute for attending lectures. The material outlined herein will be covered in greater (assessable!) detail, and extra ﬁgures, photocopies and pages will be handed out in lectures. And, while every care has been taken to ensure the accuracy of these notes, there will undoubtably be errors, which will be picked up and corrected during class – yet another reason to attend!

3

4 .

. . .2 Canonical Ensemble . . .2 Internal Energy . . 3. . . 1. . . . . . . . . .3. . . . . . . . . . . .1 Magnetic Materials . . . . . . . . 3. . .12 Identical Particles . . . . . . . . . . . . . . . . . . 2. . . . . . . . . . .3. . .) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3.1 The Boltzmann Factor . . . .8 Gibbs Paradox . . . . . . . . . . . . . . 2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1. . . .5 Multiplicity and Entropy . . . . . . . . . . . . . . . . . . .2. 9 9 10 10 11 12 13 14 15 17 18 19 19 20 21 23 25 26 27 27 28 29 30 31 31 32 32 33 35 37 37 38 3 Paramagnetism 3. . . . . . . . . . .2. . . . . . . . . 1. . . . . . . . 3. . . . . 2. . . .11 Quantum Ideal Gas . . . . . . . . .3 Multiplicity Function for a Paramagnet . . . . . .6 Multiplicity and Temperature . . . . . . . 2. . . . . . . 2. . . . . . . . . . . . . .3 Helmholtz Free Energy . . . . . . 2. . . . . . 1. . . . . .4 Multiplicity Function for a Classical Ideal Gas . . .10 Creating Entropy .13 Quantum Ideal Gas (Cont. . . . . . . . . . . . . . . . . . . .2. . . . . . . . . . . 1. . . . . 5 . . . . . . 3. . . . . . . 2. . . . . . . . . . .2 The Microcanonical Ensemble . . . . . . . 2. . . . . . 2. . .Contents 1 Microcanonical Ensemble 1. . . . . . .2 Magnetisation . . . . . . . . . . . .5 Classical Ideal Gas . . . . . . . . . . . . . . . . . . . . 2. . . .1 Microcanonical Ensemble . . . . . . . . . . . . . . . . . . . . . .1. .9 Resolution of the Gibbs Paradox 2. .7 Maxwell Speed Distribution . . . . 2 Canonical Ensemble 2. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .1 Sharpness of the Multiplicity Function . . . . . .6 Equipartition Theorem . . . . . . . . . . . .1 Partition Function . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .2 Non-interacting Two-state Paramagnet . . .1 Magnetisation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .4 Classical Statistical Mechanics .1 Mathematical Aside: Stirling’s Approximation 1. . 3. . . . . . . 1. . . . . . . . . . . . . . . . . .3 Insulators of Ions with Partially Full Shells 3. . . . . . . . . . . . . . . . . . . . . . . . . . . 3. . . . . .1 Microstates . . . . . . . . . . . . . . . . . 2. . . . . .

. . . . . . .2 Zero Temperature . . . . . . . . . . . .2 The Planck Distribution . . 7. .5. . . . . . .4. . . . . . . . . . . . . .3 Comparison with Boltzmann Statistics . . . . . . . . . . . . . .4 CONTENTS Internal Energy and Entropy . 7. . .3. . . . . . . . .5. . . . .3 3. . . . . . 7. . . . . . . . . . . . . . . . . . . . . . . . . 7. . . . .4 Grand Canonical Ensemble Thermodynamics of Diﬀusive Equilibrium: The Chemical Potential The Grand Free Energy . . .3. . . . . . . . 7. . . . . . . . . . . . . . . . . . . 4. . . 4.1 Bosons and Fermions . . . . . . . .5 Phonons ( = Quantum Lattice Vibrations) 5. . . .1 What is a Degenerate Fermi Gas? . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7. . . . . . . . . . 5. . . . . . . . . . . . . . . . . . . . . . . 7. . .6 3. . . . . 41 42 45 45 46 47 48 49 51 51 54 55 55 58 61 63 64 67 67 70 71 73 75 75 76 77 79 79 80 81 84 84 84 90 90 91 92 92 94 94 96 97 4 Thermal Radiation 4. . . 7. 7 Quantum Statistics 7. . . . .1. . . . . . .5. . . . . . . . . . . . . . . .3 Internal Energy at Zero Temperature . . . . . . 5. . . . . . . . . . . .3. . . . . . . .3 Summing Over Modes . .4. . . . . . . . . . 7. . . . 7. . . . . . . . .5. . . . . .4 Degeneracy Pressure . . . .5. . .5 Density of States in a Three Dimensional Cube .1 The Einstein Model . . . . . . .7 The Debye Model . . . . . . . 5. 7. 7. .2 6. . . . . . . . . . . . . . .3 Density of States . . . . . . . . . . . . . . . . . . . .2 Small Non-Zero Temperatures . . . . . 7. . . . . . . . . . . . . . . . . . . . . . . . . Cooling by Adiabatic Demagnetisation . .4 Classical Lattice Vibrations . . . . . . .2 Case II . . . . . . . . . . . . . . . . .3 6. . . . . . . . . . . . . . .2 Quantum Statistics . . . .1 Case I . . . . . 7. . . . . . . . . . . . . .3 Distribution Functions . Relation of Grand Partition Function to Grand Free Energy . . .4 Blackbody Radiation . . . . . . . .5 Cosmic Background Radiation 5 Phonons In Crystals 5.4 Degenerate Fermi Gas . . . . The Grand Canonical Ensemble: The Gibbs Factor . . . . . . . . . . . . . . . 6 The 6. . . . . . .Bosons . 5. . 7. . . . . . . . . . . .4. . . . . . . . . . . . . . . . .3 Debye Model of Solids . . . . . . . . . . . . . . . . . . . . 7.1 Ultraviolet Catastrophe . . 7. . . . . . . . . . . . . . . . . .3. . . . .1 Reading . . . . . . . . . . . 5.1 Indistinguishable Particles in Quantum Mechanics . .2 Quantum Harmonic Oscillators . . . . . . . . . . . . . . . .6 Energy and Momenta of Phonons . . . . . . 4. . . 4. . 5. . .Method 2 . . . . . . . . . .5 Degenerate Fermi Gases at Low Temperatures . .4. . . . . . . . . . . . . . . .4.3.5 Bulk Modulus . . . . .1 6. . . . . . . . . . . .Fermions . .Method 1 7. . . . . . . . . . . . . . . .4 Density of States in a Three Dimensional Cube . . . .8 Solid State Simulations . . . . . . . . . . . . . . . . . . . .

. . 10.5. .5. . . . . . . . . . . 11. Random Walks and Diﬀusion 10. 10.6 8 Bose-Einstein Condensation 8. . . . . . . 11. . .5 Exact Solution Of The Ising Model In One Dimension 9. . . . . . . . . . . . . . . 8. . 9. . . . . . . . . . . 10. . . . . . . . . . . . . . . . . . . . . . .1 A Brief History of Brownian Motion . . . . . . . . . . . . . .1 Heavy Fermion Metals . .2 Examples of Bose-Einstein Condensation . . . . . . . . . . . . . . . . . . . . . . .2 Distribution Function . . . . . . 9. . 8. . . . . . . . . . . . . 9.3 Mean-Field Theory . . 7 98 100 102 103 105 108 109 109 113 113 113 113 114 117 118 119 121 122 125 128 132 132 134 134 135 135 137 138 138 140 140 140 142 143 144 145 145 146 146 147 147 7.8 Universality of Critical Exponents . . . .1 Terminal Velocity . . . . . .1 Ferromagnet-Paramagnet Phase Transition . . . . . . . . . 10. . . . . . . . 9. . . . . . . . . . .5 Relaxation Time Approximation . . . . . . . 7. . 9 Magnetic Phase Transitions 9. .4. . . .6 Diﬀusion Equation and Brownian Motion . .2. . .2 Thermomechanical Eﬀect . . . . . . . . . . . .9 Low Temperature Heat Capacity of Metals . . . 10 Brownian Motion. 9. . . . . . . . . . . . . . . . . . . . . . . . . . 10. . . . . . . . 8. . . . . . .5. . . . . . . . . . . . . . . . . . 11 Transport Theory and the Boltzmann Equation 11. . . . . . . . . . . . . . . . . . . . . . . .4 Two Fluid Model of Superﬂuidity . . . . . . . . . .5 Perrin’s Determination of Avagadro’s Number from Brownian Motion . . . . . . . . . . . . . . . . . . 11. . . . . . . . . . . . . . 8. . . . . . . .4 Solid State Simulations . . . . . . . . . . . . . . . . . . . . . . . . . . . .1 Superleaks . . .8 Heat Capacity . . . . . .4 The Boltzmann Equation . . . . . . . . . .3 Frictional Forces . . . . . . .7 Fokker-Planck Equation . . . . . . . . .2 Dilute Gases of Weakly Interacting Gases 8. . . . . . 7. . .1 Transport Coeﬃcents . . . . . . . . . . . . . . . . . . . . . .1 Liquid Helium-4 (4 He) . .4 The Langevin Equation . . . . . . . . 7. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .6 Temperature Dependence of the Chemical Potential 7. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .3 Free Particle Evolution (Liouvile’s Theorem) . . . . . . . . . . . . . . . . . . . . . . 10.6 Correlation Functions and Lengths . . . . . . . . . . .2. . . . . . . . . . . . . . . . .3 Why Does Bose-Einstein Condensation Occur? . 8. . . . . . . . .5. . . . . .3 Mechanocaloric Eﬀect . . . . . . . Magnetic Susceptibility of Metals – Pauli Paramagnetism . . . . . . . . . . . . . . .1 Macroscopic Occupation of the Ground State .2 The Ising Model . . 8. . . . .3. . . . . . . . . . . . . . .4. . .6. 10. . . . . . . . . . . . . .CONTENTS 7. .7 Critical Exponents . . . .7 The Sommerfeld Expansion . . . . 11. . . . . . . 9. . . . . . . .4. . . . . . . . . . . . . . . . . . . . . . . . . .2 Random Walks . . . . . . . . . 9. . . . . . . . . . . . . . . . . . 8. .9 Mean-Field Theory Isn’t All Bad! . . . .

. .7 Diﬀusion Constant From the Boltzmann Equation . . . . . . . . . . . . . 149 . . . .8 CONTENTS 11. . .8 Ohms Law and the Drude Model For Fermions . . . . . . .6 Uniform Solution . . . . . . . . . 148 11. . . . 148 11. . . . . . .

15 1. T.1 Microstates Up until now we have only considered thermodynamic (or macroscopic) states. ch.e. atomic) composition of the systems. These are deﬁned by a small number of co-ordinates (e.g. ch. ch.V.Chapter 1 Microcanonical Ensemble Key Concepts • Microstates and ensembles • Fundamental assumption • Multiplicity function. 1 & 2 • Callen . 9 .N). We have ignored the microscopic (i. g • Stirling’s approxiation • g for an ideal gas • g for a paramagnet • Sharpness of g • g and entropy • g and temperature Reading • Shroeder. 2 & 3 • Kittel & Kroemer.

The quantum state of each oscillator is deﬁned by the quantum number n. The fundamental assumption is that all microstates in the ensemble are equally probable. one with a ﬁxed energy.3. The microstate is deﬁned by the 6N co-ordinates (q1 . Let g = g(U. g(U. . Then the ensemble average of X is X = S X(S)P (S) = 1 g X(S) S 1.10 CHAPTER 1. Shroeder when n >> 1 n! Simple derivation of the n n e √ 2πn . . . p2 .e.). The total energy of the microstate is N N ω ω U= + ni 2 i=1 1. nN ). . magnetic. . N ) be the number of microstates in the ensemble. each with frequency ω. The probability of ﬁnding the system in a particular state S is P (S) = 1 g Suppose we are interested in some macroscopic property X of the system such that X(S) is the value for the microstate S. pN ) where qi is the position and pi the momenta of the ith particle Example. . q2 . U . V. and gravitational ﬁelds are also ﬁxed. . V . n2 . ﬁxed volume. A Quantum Microstate Consider a set of N harmonic oscillators. The microcanonical ensemble consists of all possible microstates that are consistent with the constants (U.2. p1 . N. N .2 The Microcanonical Ensemble Consider a closed system. V. corresponding to the energy level (n + 1/2) ω. . i. A Classical Microstate Consider a system of N classical particles inside a ﬁxed volume V. of particles. qN . MICROCANONICAL ENSEMBLE Example. The microstate is deﬁned by the set of N integers (n1 . etc. N ) is called the multiplicity function.1 Mathematical Aside: Stirling’s Approximation n e factor n Ref: Appendix B. V. and a constant number. All external parameters such as electric.

in statistical mechanics it is suﬃcient to take ln (n!) n ln (n) − n 1. Each spin can be in the |↑ or |↓ quantum state. N↓ spins in the |↓ state (N = N↑ + N↓ ).3. . 2S = N↑ − N↓ S is the spin excess Example 1. N =3 Spin Excess (S) +3 +2 +1 0 −1 −2 −3 In general there are N! N↑ !N↓ ! ways of making a state with spin excess S. 1] = ln (n) + ln (n − 1) + ln (n − 2) + . The system has 2N possible quantum states.3.1. ln (1) n ln (x)dx 0 (x ln (x) − x)|n 0 n ln (n) − n n = n ln e n n n! = e = = Generally. . Multiplicity (g) 1 0 ↑↑↓ ↑↓↑ ↓↑↑ 3 0 ↓↓↑ ↓↑↓ ↑↓↓ 3 0 ↓↓↓ 1 ↑↑↑ . Suppose there are N↑ spins in the |↑ state. .3 Multiplicity Function for a Paramagnet Consider a system of N spins. MULTIPLICITY FUNCTION FOR A PARAMAGNET 11 ln n! = ln [n(n − 1)(n − 2) .1. ..

0) exp N log 2 − 2S 2 N −2S 2 N S N Note: 1. the total energy of the system is U = −M · B = +gµB SB 1. . . B.12 CHAPTER 1. MICROCANONICAL ENSEMBLE g(N. . In the presence of an external magnetic ﬁeld. We can’t distinguish diﬀerent microstates with the same S using macroscopic measurements. Note: 1.1 Sharpness of the Multiplicity Function log (g) 1 1 log (N !) − log (( N + S)!) − log (( N − S)!) 2 2 1 1 = ( N + S + N − S) log N − N 2 2 1 1 1 −( N + S) log ( N + S) + ( N + S) 2 2 2 1 1 1 −( N − S) log ( N − S) + ( N − S) 2 2 2 ( 1 N + S) ( 1 N − S) 1 1 = −( N + S) log 2 − ( N − S) log 2 2 N 2 N = 1 2S log ( (1 + )) 2 N 2S 2S 2 − 2 N N Now − log 2 + 1 (since log (1 + x) = x − 2 x2 + . for x << 1) Therefore log (g) and ﬁnally g(N. 2. S) g(N. S) is reduced to e−1 of its maximum value when = √1 2N 1 2. S) is the number of states having the same value of S. S) = (1N 2 N! 1 + S)!( 2 N − S)! g(N.3. g(N. N and S are the macroscopic thermodynamic variables. For large N (∼ 1023 ) the distribution is extremely sharply deﬁned ( √2N −→ 0 as N −→ ∞).

in 3N dimensional space. with 2M U . Ω1 .1) (p2 + p2 + p2 ) z y 2M x where M is the mass of the particle. From the constraint in Equation 1. The number of microstates.4. available to a single particle system is proportional to the number of possible values of (q1 . The energy of a single particle is its kinetic energy. MULTIPLICITY FUNCTION FOR A CLASSICAL IDEAL GAS 13 g(N. py .4 Multiplicity Function for a Classical Ideal Gas Consider a system of N non-interacting classical particles contained in a volume V . i i √ i 1 2M N p2 i i=1 This deﬁnes a hyper-sphere. 1 (1.1. The multiplicity is .S) width~ N S 1.1 we see that VP is proportional to the area of the surface of a 3-dimensional sphere √ of radius 2M U1 VP ∼ 4π( 2M U1 )2 For the case of N particles we have the constraint U= pi = radius r = (px . p1 ) U1 = Ω1 ∝ V · VP VP ≡ ’Volume’ of possible p1 values. pz ).

14 CHAPTER 1. and A3N = ’area’ of the hypersphere In Appendix B4 .1: Composite system with total energy U = U1 + U2 g(U ) = multiplicity of the composite system g1 (U1 ) = multiplicity of system 1 By deﬁnition g(U ) = g1 (U1 )g2 (U − U1 ) Suppose we consider the following process Initial state – 2 systems isolated (Figure 1. N ) 1. Γ(n + 1) = n!. N ) = 1 N! V h3 N A3N 1 Where N ! allows for indistinguishable particles. Shroeder shows that the surface ’area’ of a d-dimensional ’hypershpere’ of radius r is Ad (r) = 2π d/2 rd−1 Γ(d/2) Γ(z) is the gamma function. Consider a composite system with total energy. MICROCANONICAL ENSEMBLE g(U. Since N >> 1 we can write 1 V N π 3N/2 (2M U )3N/2 N ! h3N (3N/2)! ≡ f (N )V N U 3N/2 g(U.1 U1 1 U2 2 Figure 1. h3 is inserted to make g dimensionless (almost). V.2) gi (U ) = g1 (U10 )g2 (U − U10 ) . U as shown in Figure 1.5 Multiplicity and Entropy We now show that the multiplicity is an entropy function. V.

Note: ln (g(U )) has the additivity property that the absolute (metric) entropy does.6 Multiplicity and Temperature Suppose systems 1 and 2 are in thermal equilibrium and the system undergoes a reversible adiabatic process g(U ) = U1 g1 (U1 )g2 (U − U1 ) . consider a composite system C composed of two components A and B. MULTIPLICITY AND TEMPERATURE 15 U 10 1 U .e.6.2: Two systems isolated 1 2 Figure 1. V ) with the (metrical) entropy S(U.3) gf (U ) = U1 g1 (U1 )g2 (U − U1 ) This sum includes the term gi = g1 (U10 )g2 (U − U10 ) Thus gf (U ) ≥ gi (U ) hence we can use g(U ) as an empirical entropy function. i. V ). then gC ln gC = gA · gB = ln gA + ln gB This led Boltzmann to identify ln g(U.U 10 2 Figure 1. 1.3: Thermal contact – Uf = Ui = U Final state – 2 systems brought into thermal contact (Figure 1.1.

V ) = S = kB ln g(U. Kittel and Kroemer are misleading because they only deﬁne it for quantum systems. Hence. . MICROCANONICAL ENSEMBLE U1 U2 Reversible ⇒ dg = 0 Adiabatic ⇒ dU = 0 ⇒ dU1 = −dU2 0 = dg = ∂g2 ∂g1 g2 dU1 + g1 dU2 ∂U1 ∂U2 1 ∂g1 1 ∂g2 = g2 g1 dU1 − g1 ∂U1 g2 ∂U2 1 ∂g2 = g2 ∂U2 ⇒ 1 ∂g1 g1 ∂U1 N. V ) This is the Boltzmann entropy. The Boltzmann entropy can be deﬁned for both classical and quantum systems. but just a quantity that is the same for the two systems in equilibrium). The microcanonical ensemble turns out to be a very cumbersome way of calculating thermodynamic properties and only works for a very limited number of model systems.B. later we will see that it must be Boltzmann’s constant. S is the entropy. Since 1 and 2 are in thermal equilibrium 1 ∂g ∂ ln g(U ) = g ∂U ∂U is an empirical temperature (not necessarily the real temperature. At this stage we cannot say what kB is. I think Shroeder.16 CHAPTER 1. . . therefore both must be equal to a constant. But remember 1 = T ∂S ∂U V where T is the absolute temperature. we identify S with ln g and write S(U. We will shortly consider a much more powerful method . The left hand side depends only on system 1. while the right hand side depends only on system 2.

ch. ch. 16 17 .Callen .Chapter 2 Canonical Ensemble Key Concepts • The Boltzmann factor • Partition function. ch. 3 .Shroeder.Kittel & Kroemer. 6 . Z • Relation of Z to F • Classical statistical mechanics • Classical ideal gas • Gibbs paradox • Maxwell speed distribution • Equipartition of energy • Quantum ideal gas • Sackur-Tetrode equation Reading .

ε T T Energy ε 2. . that we refer to as the ’Resevoir’. with energies. Assume that the number of particles in R and S are both ﬁxed.1 The Boltzmann Factor We want to ﬁnd the probability. that a system.. Fundamental assumption of statistical mechanics All accessible states are equally probable for a closed system P ( 1) P ( 1) = = gR (U0 − 1 ) gR (U0 − 2 ) 1 exp (SR (U0 − kB ∼ 1) − SR (U0 − 2 )) since SR (U ) = entropy of R = kB ln gR (U ) we now assume 1 . CANONICAL ENSEMBLE Total system = K Constant energy Uo "Reservoir" = R Energy Uo . T is the common temperature. And similarly for state 2. 1 and 2 . In state 1 the number of states accessible to K is gK = gR+S = gR gS = gR (U0 − 1) since gS = 1 (we ﬁxed the state it is in). S. R. We suppose S is in thermal equilibrium with a much larger system.18 CHAPTER 2. U =U0 = ∂SR ∂U . therfore exp (− 1 /kB T ) P ( 1) = P ( 2) exp (− 2 /kB T ) e(− /kB T ) is known as the Boltzmann factor. P ( ). 2 << U0 so we may perform a Taylor expansion SR (U0 − ) = SR (U0 ) − But 1 T ∂S ∂U + . will be in a state with energy. 1 and 2. Thus .. Consider two possible states. for the system S.

3 Helmholtz Free Energy It’s often more convenient to work with the Helmholtz free energy which can be calculated from Z as follows F (V. 1 kB T . which is German for ’state sum’). INTERNAL ENERGY 19 where β ≡ of S). From Z = Z(V. T ) = kB T 2 ∂T = − 2.2 Internal Energy By deﬁnition U = s sP ( s) = 1 Z s s exp (−β s ) 1 ∂ Z Z ∂β ∂ = − ln Z(V.2.2. T ) ∂β ∂ ln Z(V. s. T ) = U − T S dF = −SdT − P dV so S = − ∂F ∂T V . and 1 −β e Z s P ( s ) = 1 (the idex s runs over all possible states.P =− ∂F ∂V T U = = = F + TS ∂F ∂T ∂ F −T 2 ∂T T F −T V . T ) we can calculate thermodynamic functions! 2. P( ) = Z= s exp (−β s ) Z is called the Partition Function (Z stands for Zunstandsumme.

we have derived the dependence of the Helmoholtz free energy on the partition function. CANONICAL ENSEMBLE ∂ But U = kB T 2 ∂T (ln Z)V . . . meaning e− the smallest is signiﬁcant) 0 /kB T −→ 0. We now ﬁnd this constant.4 Classical Statistical Mechanics For a system of N particles. M . the microstate of the system is deﬁned by the positions (q1 . Z −→ g0 e− 0 /kB T (because − 0 /kB T −→ −∞. T ) Using this we can also calculate the pressure directly from the partition function P = kB T ∂ (ln Z(V. each of mass.20 CHAPTER 2. F (V. . p2 . T )) ∂V 2. . . Therefore. qN ) and momenta (p1 . . pN ) of the particles. If the particles only interact via conservative forces the dynamics is described by a Hamiltonian . therefore ∂ ∂T Integrate this kB T ln Z + F T =0 V F = −kB ln Z + α(V ) T Where α(V ) is the integration constant. . so only the term with 0 where g0 is the degeneracy of the ground state term with energy kB T ln Z S(T ) −→ kB T −→ ln g0 − 0 kB ln g0 + α By our earlier deﬁnition of S we must have α = 0. . q2 . ∂F ∂T S = − V ∂ (−kB T ln Z + α(V )T ) = − ∂T ∂ = − (−kB T ln Z) + α(V ) ∂T as T −→ 0. T ) = −kB T ln Z(V.

. N Z = = i=1 n d3 p i z d3 qi 1 p2 ) exp (− 3 h 2M kB T i where . . q2 . .5. . it was introduced by Gibbs in 1875 and turns out to be Plank’s constant! 2. h is an undetermined constant (with dimensions of action) required to make Z dimensionless. . qN ) 2M i The partition function is d3 pi d3 qi 1 H(qi . CLASSICAL IDEAL GAS 21 N H= i=1 1 2 p + V (q1 . M . the integral of d3 qi is over the volume. p2 . covering all possible states. pi )) exp (− h3 kB T i=1 N Z(V. . . . The energy of the state ℘ = (p1 . V . T ) = The integral of d3 pi is from −∞ to +∞ (in each cartesian direction). conﬁned to a volume.2. V . pN ) is 1 2M N E(℘) = The partition function is Pi2 i=1 Z = s e−βEs e−β 2m s N 1 = = s PN i=1 p2 i e− 2m pi i=1 β 2 Then we convert the sum to an integral of all values of position and momentum.5 Classical Ideal Gas Consider a set of N non-interacting particles of mass.

T )) ∂V PV The ideal gas equation! U = = = ∂ ln Z ∂T 31 kB T 2 · N · 2T 3 N kB T 2 kB T 2 Equipartition of energy : There is an energy of 1 kB T associated with each 2 degree of freedom. dx exp (−αx2 ) = π α Continuing from the partition function: ln Z = N ln z 2πM 3 = N [ln V + (ln (kB T ) + ln ( 2 ))] 2 h as before P ∂F ∂V N kB T = V = N kB T = − = kB T T ∂ (ln Z(V. The ideal gas constant.315 J mol−1 K−1 . None of the above results depend on M 2. CANONICAL ENSEMBLE z = = = V h3 V d3 qi ∞ −∞ 1 d3 pi exp (− p2 ) h3 2M kB T i 3 dp exp (−p2 /2M kB T ) 3/2 2πM kB T h2 Note: 1.22 CHAPTER 2.02 × 1023 . ∞ −∞ 2.NA = 6. R = NA kB = 8. CV = Note: 3 N kB 2 1. pi . contributes equally so that it suﬃces to calculate the integral for one component and then cube it. Notice in going from the ﬁrst line to the second in the above calculation each component.

2 Proof. k 2 q 2 H0 = Hamiltonian due to all other degrees of freedom.6 Equipartition Theorem Ref: Shroeder. Z = = Z0 Z0 ∞ −∞ dq exp −kq 2 2kB T 2πkB T k 1/2 U (T ) = ∂ 1 (ln Z0 + ln ∂T 2 1 = U0 (T ) + kB T 2 kB T 2 2πkB T ) k Example 2.2. q) = and so has internal energy kB T p2 Mω 2 + q 2M 2 . H = H0 + Then. q contributes 1 kB T to the internal energy. EQUIPARTITION THEOREM 23 2.1.6.6. section 6. which has a quadratic term in the classical Hamiltonian.3 Suppose that there is a degree of freedom q. A classical harmonic oscillator has H(p.

24 CHAPTER 2. CANONICAL ENSEMBLE Figure 2.1: Photocopy – Heat Capacity at Constant Volume for H2 .

v. sect.7. is M 2πkB T 3/2 P (v) = 4π v 2 exp − M v2 2kB T vmax = v= ¯ vrms = ¯ v2 = 2kB T M 8kB T πM 3kB T M .4 The probability of a gas particle having momentum px in the x-direction is proportional to exp − By normalising we ﬁnd P (vx ) = so that ∞ −∞ 1 p2 2M kB T x = exp − M 2 v 2kB T x 2πkB T M exp − M 2 v 2kB T x P (vx )dvx = 1 In spherical polar co-ordinates dvx dvy dvz = v 2 d2 Ωv dv 2 2 2 where v =speed = (vx + vy + vz )1/2 Normalisation requires ∞ 0 dvP (v) = 1 The probability density for ﬁnding a particle with speed.7 Maxwell Speed Distribution Ref: Shroeder. 6. MAXWELL SPEED DISTRIBUTION 25 2.2.

CANONICAL ENSEMBLE max p(v) v max v v rms 2. S(T ) violates the third law of thermodynamics since as T −→ 0.26 CHAPTER 2. S is not extensive If V −→ 2V and N −→ 2N .8 Gibbs Paradox Let’s calculate the entropy of a classical gas ∂F ∂T V ∂ (kB T ln Z) ∂T kB ln Z + kB T · N 3 + ln V 2 3 1 ·N · 2 T 2πM kB T h2 S = = = S kB PROBLEMS: = 1. ∆S Sf − Si V N ln = 2 2 2 = −N kB ln 2 = − N ln V kB . S −→ 2S 2. Gibbs Paradox Take the system and insert a partition in the middle. S(T ) −→ −∞ 3.

If we ﬁx N and V and heat the system the entropy increases. N −→ 2N .2. If we partition the system the entropy does not change 2.9 Resolution of the Gibbs Paradox The above derivation of Z(V.1 3. V or T .2. 2 For the ideal gas S = N kB + In general we can increase S by increasing N .see tutorial 6. ⇒ Q = 0 . However heat is not necessary to increase entropy. • Remove the partition • No heat ﬂows into of out of the gas. There is still the problem that the entropy becomes negative at low temperatures . This is extensive.9. T ) for an ideal gas neglected the fact that the particles are indistinguishable. Prior to its theoretical derivation the Sackur-Tetrode equation was derived empirically from experimental data. 2. RESOLUTION OF THE GIBBS PARADOX Hence we have decreased the entropy and violated the second law of thermodynamics! 27 2. We should write ZN = As a result S −→ Sold − kB ln N ! Sold − kB (N ln N − N ) 1 N z N! Where we have used Stirling’s approximation. S/kB = N Note: S + ln 2 V N 2πM kB T h2 3/2 1. We have now derived the Sackur-Tetrode equation (for the entropy of a classical gas). Consider the following case of free expansion of a gas into a vacuum (see Figure 2. V −→ 2V ⇒ S −→ 2S.10 Creating Entropy 5 + ln 2 V N 3 ln T + const.

nz )/kB T ) nx =1 ny =1 nz =1 . CANONICAL ENSEMBLE inital state gas "vacuum" adiabatic enclosure Figure 2. y. in a cube of dimensions L × L × L. 0) = Ψ(x. L. z) = 0 Ψ(x.11 Quantum Ideal Gas Consider a particle of mass. ny . ⇒ W = 0 • Therefore ∆U = Q + W = 0 • But the entropy of the gas increases 2. y. y. z) = Ψ(x. z) = A sin h2 π 2M L The partition function for a single particle is E = (nx . z) = 0 Ψ(x. z) The boundary conditions are Ψ(0. y. ny . nx . z) = Ψ(L. y.28 CHAPTER 2.’s Ψ(x. M . nz are positive integers = quantum no.2: Free expansion of gas into a vacuum • The gas does not push against anything when it expands. nz ) = z= ∞ ∞ ∞ 2 2 (n2 + n2 + nz ) x y exp (− (nx . L) = 0 The solution is ny πy nz πz nx πx sin sin L L L Where A is a normalisation constant. ny . 0. y. Shroedinger’s equation is: −h2 2M ∂2 ∂2 ∂2 + 2+ 2 ∂x2 ∂y ∂z Ψ(x. y. z) = EΨ(x.

**2.12. IDENTICAL PARTICLES The spacing of the energy levels is h2 π 2M L so we can take the continuum limit ∼ z=
**

0 ∞ 2

29

<< kB T

dnx

0

∞

dny

0

∞

dnz exp (−α(n2 + n2 + n2 )) z x y

where α ≡

(πh)2 2M L2 kB T

**We may write this as z = z3 ¯ where z = ¯
**

0 ∞

dn exp (−αn2 ) π α

=

1 2

**(c.f. derivation of the partition function for a classical ideal gas) z = nQ V V ≡ L3 , and nQ ≡
**

M kB T 3/2 2π 2 h λ

Since, using the de Broglie relation, p =

KE ∼ kB T

= =

p2 2M h2 2M λ2 T h2 M kB T

⇒λ

∼

λT ∼ (thermal) de Broglie wavelength of a particle with energy kB T

2.12

Identical Particles

Consider two occupied states with diﬀerent particles ﬁgure However, if the particles are identical they should only be counted once. If there are distinct single particle states

30

CHAPTER 2. CANONICAL ENSEMBLE

N N Z1

=

i

e

−β

i

then each entry occurs N ! times. This is overcounting! We should write ZN = 1 N Z N! 1

Note: We are implicitly assuming that there are many more energy levels than particles, i.e. we are not considering the possibility of more than one particle in a level

2.13

**Quantum Ideal Gas (Cont.)
**

ZN P = = = 1 (nQ V )N N! ∂ kB T ln ZN ∂V nkB T V

**To calculate the entropy S = = = now using ZN =
**

1 N N ! (nQ V )

−

∂F ∂T

∂ (kB T ln Z) ∂T kB ln Z + kB T ∂ ln ZN ∂T

and Stirling’s approximation = = N ln (nQ V ) − ln N ! ∂ 3N ln nQ = N ∂T 2T

ln ZN ∂ ln ZN ∂T

Putting this into the above formula for the entropy, we again have the Sackur-Tetrode equation S = kB N S + ln 2 nQ V N

Chapter 3

Paramagnetism

Key Concepts

• Magnetisation of amgenetic materials • two state paramagnet – microcanonical treatment – canonical treatment • 2J + 1 state paramagnet • Brillouin function • cooling by adiabatic demagnetisation

Reading

D.V. Schroeder, SEction 3.3 and p.145-146 M.W. Zemansky, Heat and Thermodynamics, Fifth edition (Mc Graw Hill, 1968), p.446-455 Achcroft and Mermin, Solid State Physics, Ch. 31

3.1

Magnetisation

Electrons have a magnetic moment m due to their spin and due to their orbital angular momentum. For a system of N electrons or ions the magnetisation is deﬁned as

N

M=

i=1

mi

where a denotes a thermal average. 31

the moments are parallel to an external magnetic ﬁeld B Examples • electrons in a metal • ions in an insulator where the electron shell is partially full 2.1 particles (e. Paramagnets: M = χB where χ > 0 i. Diamagnets: M = χB where χ < 0 i. Ni 4. Ferromagnet: M = 0 when B = 0.32 CHAPTER 3. The Hamiltonain for a single moment is H = = = −m · B −mz Bz −mB (3. m and B are anti-parallel. The eﬀect of the ﬁeld is to tend to align the magnetic dipole moment m of each particle parallel to the ﬁeld. The energy is lower when the spin is parallel to the magnetic ﬁeld (−mB as opposed to mB). Antiferromagnets M = 0 but mi = 0 for B = 0 ↑↓↑↓↑ Examples • MnO. Examples • ions with full electronic shells in an insulator superconductor 3.e. PARAMAGNETISM 3.2 Non-interacting Two-state Paramagnet Consider a system of N spin.1) since we take B to point in the z-direction. pointing in the z-direction.e. for T < TC ↑↑↑↑↑↑ TC is the critical temperature. electrons) that are localised (i.e.g.1. FeO 3. 2 cannot move) in the presence of a constant magnetic ﬁeld B. Examples • Fe. . Co.1 Magnetic Materials 1.

3 The entropy is S(U.79 × 10−5 eV /T (3. NON-INTERACTING TWO-STATE PARAMAGNET 33 For spin.2.1 particles. 2 g = 2.4) (3.5) . and N↑ is the number of up spins.3) 3.1 operator. µB ≡ = = eh = Bohr Magneton 4πme 9. The multiplicity of the system is g(U.B ∂N↑ ∂S ∂U ∂N↑ ∂S 1 − 2µB ∂N↑ (3. The temperature is given by 1 T = = = ∂S ∂U N! N↑ !N↓ N.2) m = −gµB S The total energy of the system is U = µB(N↓ − N↑ ) = µB (N − 2N↑ ) where N = N↑ + N↓ .27 × 10−24 J/T 5.1 Microcanonical Ensemble We now ﬁnd M as a function of B and the tempearature T using the microcanonical ensemble. . The magnetisation M is the total magnetic moment of the whole system M = µ(M↑ − N↓ ) = − U B (3. . and g is the g-factor or gyromagnetic ratio. where S is the spin. N ) = as stated in Section 1.01 . N ) = N ln N − N↑ ln N↑ − (N − N↑ ) ln(N − N↑ ) kB where we have used Stirlings approximation.2.3. mz can have eigenvalues ±µ so the allowed energy levels 2 are E = ±µB For electrons.

all the moments are parallel to the ﬁeld . and their spins are randomly aligned.4 and N = N↑ + N↓ . consider 1 kB ∂S ∂N↑ = N − ln N↑ − 1 + ln(N − N↑ ) + 1 ln ln N − N↑ N↑ N↓ N↑ = = (3.6) So that from Equations 3. PARAMAGNETISM To ﬁnd the mean magnetic moment M/N . M N = = µ(N↑ − N↓ ) N↑ + N↓ µ(1 − 1+ 2µB 1 − exp − kB T µ 2µB 1 + exp − kB T µB kB T (3.34 CHAPTER 3.6 N↓ 2µB = exp − N↑ kB T and thus from Equation 3. because the electrons are so energetic tat the diﬀerence between the energies of the spin up and down down states becomes negligible.e. Notice as T → ∞.7) N↓ N↑ ) N↓ N↑ = Hence. Suppose µB >> kB T (low temperature / high ﬁeld limit) then M = µN i.5 and 3. Suppose µB << kB T (the high temperature / low ﬁeld limit) then M µ2 = NB kB T which is Curies law. M = µN tanh Check the high and low temperature limits: 1. M → 0. 2.

e−βEs e s −βµB z(B.B (µB/kB T )2 cosh2 (µB/kB T ) (3. T ) = = + eβµB µB = 2 cosh kB T The internal energy is U (T ) = = kB T 2 ∂ (ln Z)B ∂T ∂ ln cosh N kB T 2 ∂T µB sinh kB T 2 cosh µB kB T µB kB T µB kB T µB kB T = −N kB T 2 · = −N µB tanh This agrees with the microcanonical ensemble.9) 3. .2. T )N where z is the partition function for a single magnetic moment. T ) = z(B.8) N.3.1 dU dT N kB µB kB T (3.2 Canonical Ensemble We now recalculate our result using the Canonical Ensemble.4) is given by U (T ) = −M B 35 = −N µB tanh Heat capacity in a constant ﬁeld is CB (T ) = = These are shown in Figure 3. Notice that this is a lot quicker and easier than the microcanonical formulation. The partition ﬁunction Z(B.2. NON-INTERACTING TWO-STATE PARAMAGNET The internal energy (again from Equation 3.

2 M/µ N 0 −0.8 0.05 0 0 1 2 3 4 kT/µ B 5 6 7 8 Figure 3.35 0.8 −1 −10 −8 −6 −4 −2 0 kT/µ B 2 4 6 8 10 Specific Heat of a Two−State Paramagnet 0.1: Heat Capacity and Magnetisation of a Two-state Paramagnet .36 CHAPTER 3.1 0.45 0.2 0.4 −0.3 0.25 CB/Nk 0.4 0.15 0.4 0.6 0. PARAMAGNETISM Magnetization of a Two−State Paramagnet 1 0.2 −0.6 −0.

related to the fact that Hund’s rule says that each electron should be placed in a separate state with 1 parallel spins. the total angular momentum vector J = L + S and the magnetic quantum number MJ which can take 2J + 1 possible values in the range of −J. −J + 1. . INSULATORS OF IONS WITH PARTIALLY FULL SHELLS 37 3. Cr2+ and Mn4+ . J. The state is completely speciﬁed by L.3.3.1 case) 2 E(MJ ) = = where the Land´ g-factor of the ion is e g(JLS) = 1 L(L + 1) − S(S + 1) 1 (g0 + 1) − (g0 − 1) 2 2 J(J + 1) −mB g(JLS)µB MJ B (3. 3.html) are used to deterermine the basic electron conﬁguration. and g = g0 since J = S. and Fe3+ has 5 electrons in its outer orbital.gsu. 5 For Fe3+ . (This is very similar to the azimuthal angular momentum m in a hydrogen atom. the electrons in the outermost atomic orbitals (usually d-orbitals) have spin S and orbital angular momentum L.) Hund’s rules (see http://hyperphysics.1 Partition Function Z(B) = s e−βEs z(B)N = where z(B) is the partition function for a single magnetic moment and we assume they do not interact. each with spin.002319 is the electron g-factor. .phy-astr. S. MJ is −g(JLS)µB MJ and that the allowed energies are (similar to the spin.edu/hbase/atomic/hund.S. It can be shown that in a magnetic ﬁeld B = B z that the magnetic moment of ˆ an ion with quantum numbers J.3. Fe2+ . J − 1. 5 Hence J = 2 . only now we consider the total angular momentum.10) g0 = 2. . L. one can calculate that L = 0 and S = 2 . .3 Insulators of Ions with Partially Full Shells In solids containing ions such as Fe3+ . MJ =J z(B) = MJ =−J exp(aMJ ) .2 .

38 where a = gµB B kB T CHAPTER 3. the magnetic moment in the state |JMJ is −gµB MJ as stated at the start of this section.12) Note that there are 2J + 1 terms.14) (3.3.2 Magnetisation If the magnetic ﬁeld is in the z-direction. The magnetisation is M N = MJ 1 (−gµB MJ ) e−βE(MJ ) z gµB MJ B MJ exp − z kB T = = M −gµB 1 kB T z MJ ∂z ∂B T ∂ = kB T N (ln z) ∂B 1 ∂a ∂ a = kB T N ln sinh (J + )a − ln sinh( ) ∂B ∂a 2 2 and thus 1 1 1 a M = N gµB (J + ) coth (J + )a − coth( ) 2 2 2 2 We often write M = N gµB JBJ (a) (3.11) (3. We now use the fact that xn = 1 − xN 1−x 2J n z(B) = = = = e−aJ n=0 (ea ) 1 − e(2J+1)a e−aJ 1 − ea −aJ e − e(J+1)a ea/2 e−a/2 − ea/2 1 sinh((J + 2 )a) a sinh( 2 ) 3.13) . PARAMAGNETISM z(B) = = e−aJ + e−a(J−1) + · · · + +ea(J−1) + eaJ e−aJ 1 + ea + e2a + · · · + e2aJ N −1 n=0 (3.

.3. for J = 1 spin. check the limits: 1. INSULATORS OF IONS WITH PARTIALLY FULL SHELLS where BJ (a) = N gµB 1 1 1 a (J + ) coth (J + )a − coth( ) J 2 2 2 2 39 (3. coth (J + 2 )a → 1 i.15) is known as the Brillouin function. Again.e. Low temperature / high ﬁeld a= and g = 2 it reduces to the gµB B >> 1 kB T M → N gµB J 1 1 coth( 2 a) → 1.16) The Brillouin function can be tested experimentally on crystals such as Fe2 (SO4 )3 ·(NH4 )2 SO4 · 24H2 O which have crystal structures such that the magnetic ions (in this case Fe3+ ) are very isolated from one another and so the magnetic dipoles interact very weakly with one another.2 result. High temperatures and low ﬁelds a << 1 For small x << 1. coth x = M N gµB 1 (J + ) 2 1 x + x 3 + .3. all the magnetic moments are aligned parallel to the ﬁeld.. . and a= gµB B kB T 1 2 Although not imediately obvious. 2. 2 a + a 6 ≈ = = 1 1 1 1 + (J + )a − 1 2 2 (J + 2 )a 3 1 1 1 a 1 − + (J + )2 − a a 3 2 4 1 J(J + 1)a 3 J(J + 1)B 3kB T So M = N (gµB )2 which is Curie’s Law (3.

40 CHAPTER 3.2: Photocopy – Plot of magnetization per magnetic dipole . PARAMAGNETISM Figure 3.

17) Hence. T ) Thus. T ) = kB f ( gµB B kB T (3. z(a) = sinh((J + 1 )a) 2 1 sinh( 2 a) 1 1 1 1 1 1 S = ln sinh((J + )a) −(J+ ) coth (J + )a) −ln sinh( a) + coth( a) kB 2 2 2 2 2 2 (3. T ) ∂T F ≡ U − T S = −kB T ln Z(B.3. we can show ∂ ln Z(B. S=− and so S kB = ln Z(B.3.3 Internal Energy and Entropy U (T ) = −M B We also have U (T ) = kB T 2 As before. INSULATORS OF IONS WITH PARTIALLY FULL SHELLS 41 3. T ) + kB T U kB T MB ln Z − kB T ∂ ln Z(a) ∂B ∂ ln Z(a) − a ln Z(a) ∂a ln Z(a) − B ∂ ln Z(B. T ) ∂T F T B = ln Z + = = = So the entropy is an increasing function with a: S(B.3. in an adiabatic process (S is ﬁxed) and if B decreases then T must decrease too.18) As a → 0 (T → ∞): z(a) → 2J + 1 As a → ∞ (T → 0) z(a) → eJa S → kB (Ja − aJ) = 0 S → kB ln(2J + 1) .

fixed 2 0 temperature Figure 3. . the ﬁnal temperature is T Tf = Ti Bf < Ti Bi One might hope that by letting Bf → 0 we can make Tf → 0.3.42 CHAPTER 3.4 Cooling by Adiabatic Demagnetisation The material to be cooled (e. The magnetic ﬁeld is increased to a ﬁeld value Bi 2. The ﬁeld is reduced to Bf The entropy S( B ) must remain constant. The system is adiabatically isolated 3. 1. at suﬃciently low temperatures.fixed high B .3: Cooling by adiabatic demangetisation process 3. The system is held at constant temperature T = Ti . Using this method in 1933-1935. Jowever. Hence. three diﬀerent groups reached temperatures in the range 5mK to 350mK. PARAMAGNETISM S = entropy K Bln(2J+1) 1 low B . liquid helium) is in thermal equilibrium with a paramagnetic crystal. T The minimum temperature that can be reached is Tmin ∼ J where J ∼the typical interaction energy betwen the magnetic moments Note: Don’t confuse this J with the total angular momentum J! This cooling method was ﬁrst proposed in 1926 independently by Gianque and Debye.g. the interactions between the magnetic moments in the magnetic crystal become important and the relation S = S( B ) no longer holds.

In 1956. Simon and Kurti reached 10−5 K using nuclear magnetic moments.3.3. INSULATORS OF IONS WITH PARTIALLY FULL SHELLS 43 The initials temperatures were T ∼ 1K obtained by rapidly evaporating He4 . .

44 CHAPTER 3. PARAMAGNETISM .

(4. The total electromagnetic energy in the box must then be inﬁnite.4 Kittel & Kromer. . when we open the oven door we don’t get blasted with an inﬁnite amount of energy. 45 .1 Ultraviolet Catastrophe Consider classical electromagnet waves conﬁned to a box of ﬁxed volume.1) Each mode is a harmonic oscillator. so something must be wrong with this model. There are an inﬁnite number of modes of vibration for the electromagnetic waves. V = L3 . By the equipartition theorem each mode 1 must have an average energy of 2 kB T . 2. 3. Ch 4 4. However.Chapter 4 Thermal Radiation Key Concepts • The Ultraviolet Catastrophe • The Planck Distribution • Summing Over Modes • The Planck Spectrum • Black-body Radiation • Cosmic Background Radiation Reading Schroeder. . . with wavelengths λn = 2L n n = 1. Section 7.

4) 1 − e kB T kB T 2 hf hf 1 ∂Z Z ∂T hf (4. The partition function for the single oscillator is Z = = The average energy is U = = ∞ s=0 e kB T 1 −shf (4. THERMAL RADIATION n=1 n=2 L Figure 4.1: Modes of a harmonic oscillator within a box of width L 4.6) The average number of quanta of energhy hf is then the total energy divided by hf n(f ) = 1 U = hf hf e kB T − 1 (4.46 CHAPTER 4. hf kB T . . hf n(f ) e kB T 1.7) e kB T − 1 This is the Planck Distribution. Suppose that an oscillator with frequency f can only have discrete energies Es = shf s∈N (4.2 The Planck Distribution The solution to the ultraviolet catastrophe led to the birth of quantum mechanics.2) This is ignoring the zero point energy.3) (4.5) (4. These modes are “frozen out” and don’t contriubute to the total energy of the system. For high frequency modes.

.11) (4. In one dimension the allowed wavelengths are λn = 2L n n = 1.3. hc |n| n = (nx . 2. 3. py .15) . and z components of the momentum. . . ny .3 Summing Over Modes We now ﬁnd the total energy in the box using the Planck Distribution. The momenta of these wavelengths are pn = and the energ of each mode is En = pn c = In three dimensions 2 E = |p| c = c p2 + p2 + pz y x 1 2 h h = n λn 2L (4.10) where px . nz ) E(n) = 2L (4. .8) hc n 2L (4. 2. . SUMMING OVER MODES 47 4. . and are given by h px = 2L nx h py = 2L ny h pz = 2L nx nx .14) 2 n for large L we can convert the sum to an integral → ∞ 0 n 1 4π 8 n2 dn U= hcπ L n3 e 2LkB T − 1 hcn −1 dn (4. pz are the x. y. 3.13) (4.4. The total energy is then U = = 2 n ε(n)n (ε(n)) 1 hc |n| hc|n| L e 2LkB T − 1 ∞ 0 (4.9) (4. nz = 1.12) Each mode(photon) can have two possible polarisations. ny .

A blockbody emits the same photon spectrum as does a hole in a box at the same temperature.48 we make a change of variables to CHAPTER 4. It has a maximum at ε = 2.2: A hollow box and a blackbody in thermal equilibrium We can see this by considering a blackbody and a hole in a box with equal area and in thermal equilibrium. If the blackbody does not emit the same .82kB T (Wien’s law). perfectly absorbing) surface at a ﬁxed temperature T . Figure 4.e. Note that V ∼ T 4 .4 Blackbody Radiation Blackbody Radiation is the photons emitted by any non-reﬂecting (“black”.18) U The integral in Eqn 4. doubling 15 U T increases V by a factor of 16. ∂T approaches zero as the temperature goes to zero. THERMAL RADIATION ε= U = V ∞ 0 hcn .17) u(ε) ≡ (hc) e 3 ε kB T Here u(ε) is the spectrum or energy density per unit photon energy. By making another change of variables.18 evaluates to π . Hence. i. which is consistant with the third Law of Thermodynamics. 4. V = L3 2L ∞ 0 8π (hc) e 3 ε3 ε kB T −1 dε = 8π u(ε)dε ε3 (4. Also the speciﬁc heat CV (T ) = ∂U V ∼ T 3 . we can change the spectrum into the form ε x = kB T U V = 8π (kB T ) (hc) 3 4 −1 4 0 ∞ x3 dx ex − 1 (4.16) (4.

19) 1 The factor of 4 comes from a geometric calculation. Eqn 4. Then there will be a net ﬂow of energy from one emitting more energy to the one emitting less energy.20) (4. is cU P = A 4V (4.67 × 10−8 2 2 3 c2 15h m K (4. Substituting Eqn 4. there can be no nett ﬂow of energy between the two objects. since the two objects are still in thermal equilibrium. This was important because it provided evidece for spatial inhomogenous regions needed in the early universe to form galaxies. Hermann and Gamow as being a remnant of the “big bang”. But since the two are in thermal equilibrium. This argument can be extended to every frequency range because we can always insert a ﬁlter between the box and the blackbody that blocks a certain frequency range.002K and the deviation from the Planck spectrum is less than 0. They originally thought it was noise due to pigeon droppings in their radio telescope.5.728 ± 0. we get P = σT 4 A 4 2π 5 kB W σ= = 5. then there will be a nett ﬂow of energy from the object which emits less energy in the blocked range. was discovered empirically in 1879. there can be no nett energy ﬂow between the two objects. COSMIC BACKGROUND RADIATION 49 spectrum as the box. Again. and one emits more energy in the range of frequencies blocked.20. In 1989. then once the ﬁlter is in place. and now that the ﬁlter is in place it is blocking more energy from one object than the other. The power per unit area emitted by the hole. since there was no nett ﬂow before the ﬁlter was put in place. the Cosmic Background Explorer (COBE). a NASA satellite. It was ﬁrst observed accidentally in 1964 by Penzias and Wilson. and so also the blackbody.18 into the formula for the power per unit area. Stefan’s Law. . In 1992 using the diﬀerential microwave radiometer on COBE temperature ﬂuctuations of 30µK on an angular scale of 10 degrees was found. found that the cosmic bacground radiation has the spectrum of a blackbody with a temperature T = 2. The cosmic background radiation is incredibly uniform and isotropic.21) σ is known as the Stefan-Boltzmann constant.4. If the two were in thermal equilibrium before the ﬁlter is placed between them. Thus the radiation emitted by a blackbody has the same spectrum as a box at the same temperature. The cosmic background radiation are the photons which were last scattered oﬀ electrons 300000 years after the beginning of the universe. They recieved the Nobel prize in 1978. 4.5 Cosmic Background Radiation Cosmic background radiation was predicted in the late 1940’s by Alpher.005%.

50 CHAPTER 4.4: False-color maps . THERMAL RADIATION Figure 4.3: Cosmic Background Radiation Figure 4.

D. 2nd Ed.Chapter 5 Phonons In Crystals Key Concepts • Einstein model • Failure of classical statistical mechanics • Dulong-Petit Law • Debye model • Classical lattice vobrations • Phonons (= quantum lattice vibrations) Readings D. Schroeder. We can make small displacements of each atom in 3 diﬀerent directions. Thermal Physics. Simulations for Solid State Physics. each atom can be viewed as 51 . Programs a born and debye 5. p 8-10 Silsbee and Dr¨ger. Mahon. Many Particle Physics. The neighbouring atoms will cause a restoring force to make the atom tend towards it’s original equilibrium position.5 Kittel & Kromer.V.1 The Einstein Model Consider an isotropic crystal consisting of N atoms. Ch 4 Callen..7 G. Section 7. Section 16. As a ﬁrst approximation.

PHONONS IN CRYSTALS being described by 3 independent harmonic oscillators. This presented a major theoretical problem in the early 1900’s and was solved by Einstein in 1907.52 CHAPTER 5.4) These values for the internal energy and speciﬁc heat are the Dulong-Petit limit. by the equipartition theorem each quadratic term in the hamiltonian contributes 1 2 kB T to the internal energy so U (T ) = = CV (T ) = 3N kB 1 3N × 2 × kB T 2 3N kB T (5. each with the following hamiltonian H (p.2) (5. q) = mω 2 2 1 2 |p| + |q| 2m 2 (5.1) The crystal then consists of 3N harmonic oscillators. It is only observed at high temperatures.3) (5. Classicly. .

1: Photocopy – Measured Heat Capacities . THE EINSTEIN MODEL 53 Figure 5.5.1.

54

CHAPTER 5. PHONONS IN CRYSTALS

5.2

Quantum Harmonic Oscillators

We now consider the each atom in a crystal as 3 indpendent quantum harmonic oscillators. The energy of each harmonic oscillator is En = nhf n = 0, 1, 2, 3, . . . f= ω 2π (5.5)

1 Here we are ignoring the zero point energy 2 hf . The partition function of the crystal is thus

Z = z 3N z= =

∞ n=0

(5.6) (5.7) (5.8)

e

−nhf kB T

1 1 − e kB T

hf

**The internal energy of the crystal is thus U = = The speciﬁc heat is ∂U ∂T
**

hf kB T

hf

kB T 2

hf

∂ ∂ ln Z = 3N kB T 2 ln z ∂T ∂T 3N hf

(5.9) (5.10)

e kB T − 1

2

hf

e kB T

2

CV (T ) =

= 3N kB

V

(5.11)

e kB T − 1

hf kB T

**Consider the high and low temperature limits set x to CV (T ) = 3N kB x2 ex (ex − 1)
**

2

and we get (5.12)

In the high temperature limit, where kB T CV (T ) = 3N kB 3N kB

hf , x x2 e x (ex − 1) x2 (1 + x)

2

**1. Using this fact we get
**

2

(5.13) (5.14) (5.15) (5.16)

CV (T )

x+ x 2 3N kB (1 + O(x)) 3N kB

2

This is the Dulong-Petit limit for the speciﬁc heat, so this agrees in the classical limit with the Einstein model. For the low temperature limit, where

**5.3. DEBYE MODEL OF SOLIDS kB T hf , x 1. Using this fact we get CV (T ) = 3N kB x 2 ex (ex − 1)
**

2

55

(5.17) (5.18)

3N kB x2 e−x CV (T ) 3N kB

hf kB T

2

e kB T

−hf

(5.19)

This approximation of the speciﬁc heat approaches zero as the temperature T 1 12 approaches zero. (The e− T goes to zero quicker than the T term goes to inﬁnity.) This result is consistant with the third Law of Thermodynamics. However, it is observed experimentally that as the temperature approaches zero, the speciﬁc heat is of the order of T cubed. This suggests that low energy lattice vibrations (phonons) may be important.

5.3

Debye Model of Solids

The problem with the Einstein model is that it ignores that the atoms in a crystal do not vibrate independently of each other. If one atom moves, it’s neighbours will also move. The Debye model takes this into account. Sound waves are one possible crystal vibration. The obey f λ = cs = speed of sound, which corresponds to the “dispersion relationship” 2π (5.20) λ k is known as the wavevector. For each wave within the crystal there are 3 possible polarisations. Two transverse and one longitudinal. In transverse waves the motion of the atoms is perpendicular to the motion of the wave, while for the longitudinal wave the particles oscillate in the direction of the waves propogation. For simplicity we assume that the speed of the waves propogation is the same in each polarisation. Within the crystal there are a total of 3N allowed k values. ω(k) = cs |k| |k| =

5.4

Classical Lattice Vibrations

We consider a simple model, the monoatomic linear chain. This consists of a periodic chain of N atoms of mass M with an equilibrium spacing of a. Let qn be the deviation of the nth atom from it’s equilibrium position qn = xn − na (5.21)

**The potential energy should only depend of qn+1 − qn . We only consider the forces between neighbouring atoms. K U (q1 , q2 , . . . , qn ) = 2
**

N n=1

(qn+1 − qn )

2

(5.22)

56

CHAPTER 5. PHONONS IN CRYSTALS

Figure 5.2: Periodic chain of atoms at a distance a from each other Here we are assuming that the forces between the atoms follow Hooke’s law, and act like springs with a spring constant K. The classical hamiltonian of the system is H(p1 , q1 , p2 , q2 , . . . , pN , qN ) = K p2 2 N + (qn+1 − qn ) 2M 2 n=1

N

(5.23)

**We want to seperate this into normal modes of vibration. To do this we introduce two new variables 1 qk ≡ √ N
**

N

e−ikan qn

n=1 N

(5.24) (5.25)

1 pk ≡ √ N

eikan pn

n=1

Since the chain of atoms is periodic, q1 = qN . Thus k takes the values k = 2πm m = 1, 2, . . . , N . To convert back to the original mode from a the normal modes we use 1 qi = √ N 1 pi = √ N Using the normal mode form we get

N 2 pi = n=1 k

eikan qk

k

(5.26) (5.27)

e−ikan pk

k

pk p−k

(5.28) (5.29)

N

qn qn+m

n=1

= =

1 N

k

qk q k

kk n

ein(k+k )a eimak

(5.30) (5.31) (5.32)

qk q−k eimak

38) ω(k) = This is the dispersion relationship. .5. The hamiltonian in terms of the normal Figure 5.35) = = n K 2 m 2 k qk q−k 2 − eika − e−ika ω(k)2 qk q−k k ω(k)2 = = 2K (1 − cos ka) m 4K ka sin2 m 2 4K sin m ka 2 (5. According to quantum mechanics the energy of each normal mode should be quantised in units of ω(k). That is.4.37) (5. Eqn 5. they are independent harmonic oscillators.33) (5.36) (5.3: The dispersion relation for a crystal modes is H(pk . We see from the hamiltonian.39) For k 1 a ω(k) vs k = k ak m (5. it is usually easier to consider k ranging from −π to π . qk ) = k pk p−k + mω(k)2 qk q−k 2M (5.39 that the a a excitations (normal modes) with diﬀerent wavevectors do not interact with each other. CLASSICAL LATTICE VIBRATIONS K 2 (qn − qn+1 ) 2 57 (5.34) (5. Because the dispersion relationship is symetrical about the origin.40) vs is the speed of sound within the medium.

They have the commutator relationship ˆ ˆ a.41) ˆ ˆ a and a† are dimensionless quantities. N |0 (5. a † † (5.44) (5.5 Phonons ( = Quantum Lattice Vibrations) 1 2 We can quantise the normal modes of the crystal by introducing the operators ak ≡ ˆ a† ≡ ˆk mω(k) 2 mω(k) 2 qk + ˆ 1 2 i ˆ p−k mω(k) i pk ˆ mω(k) (5.42) mω 2 x2 ˆ p2 ˆ + 2m 2 (5.43) (5.50) qk − ˆ . a] = 0 = a . PHONONS IN CRYSTALS Review: Creation and Annihilation Operators for Harmonic Oscillators The hamiltonian of a harmonic oscillator is H= The commutator of x and p is ˆ ˆ [ˆ. p] = i x ˆ we introduce two new operators a and a† as ˆ ˆ a≡ ˆ ˆ a† ≡ mω 2 mω 2 x+ ˆ x− ˆ i ˆ p mω i p ˆ mω (5.58 CHAPTER 5.46) ˆ In terms of the new operators a and a† the hamiltonian is ˆ a† a + ˆ ˆ 1 2 ω (5.45) (5.48) 5.49) (5.47) If |0 is the ground state of the oscillator then 1 a† ˆ |n ≡ √ N is the nth excited state. a† = 1 a ˆ ˆ ˆ [ˆ.

. nk2 .5.55) . ak ] = 0 a† .54) which has the energy eigenvalues N E(nk1 . .51) (5. PHONONS ( = QUANTUM LATTICE VIBRATIONS) 59 These are harmonic oscillator raising and lowering operators for each normal mode k.53) a ˆ [ˆk . ak ˆ ˆ† = δkk (5. .52) (5.5. a† ˆk ˆk The quantum hamiltonian becomes ˆ H= k =0 ˆk ˆ ω(k) a† ak + 1 2 (5. nkN ) = j=1 ω(kj ) nkj + 1 2 (5. They have the commutation relations ak . .

4: Photocopy – How does this relate to a 3D crystal? .60 CHAPTER 5. PHONONS IN CRYSTALS Figure 5.

5.5: Experimental setup for determining the phonon dispersion relation from neutron scattering From conservation of momentum and energy we get the relations k = pi − pf ω(k) = Ei − Ef (5.6. Figure 5.57) .6 Energy and Momenta of Phonons A phonon with a wavevector k has a momentum p = k and an energy E = ω(k). ENERGY AND MOMENTA OF PHONONS 61 5.56) (5. The dispersion relations of phonons within a crystal can be determined from inelastic scattering of neutrons.

62 CHAPTER 5.6: Photocopy – Al is FCC . PHONONS IN CRYSTALS Figure 5.

65) e e k 3 dk cs |k| kB T −1 To simplify this we change the integration variable to x≡ hcs k kB T (5.7 The Debye Model For each phonon polarisation there are N possible k values. the internal energy of a crystal is U (T ) = k.60) k.α ωα (k) e ωα (k) kB T −1 (5. we can convert a sum over k into an integral over k by making the substitution → d3 k |k|<kD L 3 2π (5.7.63) k Using the Debye assumptions the internal energy is now U (T ) = U (T ) 4π cs = 3 V (2π) d3 k L 2π kD 0 3 cs |k| kB T cs |k| −1 (5.62) In general.66) . since N is very large. For each polaristion there are N allowed k values. The dispersion relationship is ωα (k) = cs |k| 2.58) Here α denotes the polarisation of the phonon.α To continue further analytically we now ise the Debye assumptions. the Debye wavevector which is given by kD = 2π L 3 (5.59) Where ρ(ε) is the density of states of the phonons.61) 3N 4π (5. These are 1. In general.64) (5. THE DEBYE MODEL 63 5.5. so |k| < kD . which is ρ(ε) ≡ δ (ε − ωα (k)) (5. This can be also be written as U (T ) = 0 ∞ dε ρ(ε) e kB T − 1 ε (5.

where T TD .68 with −1 inﬁnity. ∞ 0 x3 dx ex − 1 (5.64 CHAPTER 5.67) TD is called the Debye temperature. The internal energy then simpliﬁes to U (T ) V 9N kB T 4 1 3 TD 3 = 3N kB T = TD T 3 (5. standing and traveling wave packets. which is what is observed experimentally.71 evaluates to low temperature is thus CV (T ) = 12π 4 5 π4 15 . you can investigate the behaviour of standing and traveling waves. For the low temperature limit. In this case the internal energy simpliﬁes to 9N kB T 4 U (T ) = 3 V TD The integral in Eqn 5. the eﬀects of impurities in the material. 3 and 4. the integral in Eqn 5. we can replace the upper limit of the integral in Eqn 5.71) The speciﬁc heat of the crystals at 3 T TD N kB (5.68 can be 0 x2 dx. because (ex − 1) → e−x is very small and so as x approaches inﬁnity there will be no signiﬁcant contributions to the internal energy from the higher x values. 5. PHONONS IN CRYSTALS The upper limit of the integral is now xmax = TD hcs kD ≡ kB T T (5.8 Solid State Simulations Two programs in the Solid State Simulations package are useful for investigating the concepts of crystal vibrations and phonons.65 becomes U (T ) 9N kB T 4 = 3 V TD In the high temperature limit.68) TD .72) Here we have the speciﬁc heat being proportional to the temperature cubed.70) This is the Dulong-Petit limit. After making the change of variable Eqn 5. The born program simulates a one dimensional chain of atoms. Suggested settings to look at are presets 1. so the Debye model agrees with the Einstein model and experiments at high temperatures. By controlling the initial conditions of the chain.69) (5. where T approximated by TD T TD T 0 x3 dx ex − 1 (5. The debye program looks at the eﬀects of phonons in a . These programs are born and debye.

. calculated by monte carlo methods. SOLID STATE SIMULATIONS 65 material. the density of modes from preset 6. and the heat capacity and density of modes for aluminium from preset 8. The left display shows the dispersion relationship for a material along the desired direction within the material. the heat capacity or the internal energy of the material. lead and aluminium.5. so that the values calculated by the program can be compared to actual data. preset 7. Suggested settings to look at are the heat capacity from preset 1.8. The program also includes experimental data from copper. The right display can show the density of modes.

8: Photocopy – Debye Temperatures .7: Photocopy – The Debye prediction for heat capacity Figure 5. PHONONS IN CRYSTALS Figure 5.66 CHAPTER 5.

67 . Sections 3.1.1 Kittel & Kroemer.1 Thermodynamics of Diﬀusive Equilibrium: The Chemical Potential Consider an adiabatically isolated system which is seperated by a movable.5. 5.Chapter 6 The Grand Canonical Ensemble Key Concepts • Chemical potential and diﬀusive equilibrium • The relation between chemical potential and the Gibbs free energy • The grand potential • The Gibbs factor • The grand partition function Z • The relation of Z to the grand free energy Reading Schroeder. permeable membrane across which energy transport is possible. 7. Ch 5 6.

so substituting this into Eqn 6. VA . NA ) + SB (UB . By a ∂S similar argument.5) (6.Va Ub . UA .7) ∂S However.7 and noting that we already know the temperatures to be equal.N . THE GRAND CANONICAL ENSEMBLE Ua . We can use this to determine the conditions for equilibrium.1: Two systems in diﬀusive equilibrium The following conditions hold within this system Ntotal Vtotal Utotal Stotal = NA + NB = a ﬁxed constant = VA + VB = a ﬁxed constant = UA + UB = a ﬁxed constant = SA (UA . Taking the derivative of the total entropy with respect to the internal energy of A we have ∂Stotal ∂UA = = ∂SB ∂UB = ∂SA ∂UB ∂SB + ∂UA ∂UA ∂UB ∂SB ∂SA − ∂UA ∂UB ∂SA ∂UA (6. the temperature of the two systems is equal.2) (6.6) 1 ∂S But we know that T = ∂U V. .68 CHAPTER 6.Nb . Stotal .1) (6. and so they are in thermal equilibrium. the fact that total = 0 implies that ∂VA ∂SA ∂SB = ∂VA ∂VB (6. VA . NB ) (6.4) In equilibrium the total entropy.6 we ﬁnd that if the two systems are in equilibrium.3) (6. UB . So the derivative of the total entropy taken with respect to any of these variables must be zero.Vb Figure 6. NB . VB . so making this substition into Eqn 6.Na . VB .N . TA = TB . must be a maximum as a function of NA . the we know that the pressure is P = T ∂V U.

Figure 6.V (6. If the two systems are not in equilibrium the one ∂S with the larger value of ∂N will tend to gain particles.8) This is the condition for diﬀusive equilibrium. We deﬁne the Chemical Potential µ ≡ −T ∂S ∂N (6.9) (6.6. From the deﬁnition of the chemical potential it follows that T ds = dU + P dV − µdN and so we ﬁnd that µ= ∂U ∂N (6.V At equilibrium µA = µB . since it will thereby gain more entropy than the other system loses. THERMODYNAMICS OF DIFFUSIVE EQUILIBRIUM: THE CHEMICAL POTENTIAL69 we ﬁnd that the pressure of the two systems are equal. we ﬁnd that ∂Stotal ∂NA implies that ∂SB ∂SA = ∂NA ∂NB (6.12) S.2: Particles move from a system with high chemical potential to systems with a lower chemical potential Particles ﬂow from the system with the higher chemical potential into the system with the lower chemical potential. PA = PB . Again using a similar argument.10) U. similar to the way heat ﬂows from the system with the higher temperature into the colder system.1.11) . which is where there is no nett transport of particles between the two systems. and so they are in mechanical equilibrium.

we get G = Nµ (6.19) We deﬁne the grand free energy as Using the fact that T dS = dU + P dV − µdN We get dΦ = −P dV − SdT − N dµ (6. 6. must be an intensive quantity. the temperature and pressure. V.15) (6.P is the chemical potential. and since the other variables that the Gibbs free energy depends on. Consider the Gibbs free energy G ≡ U + PV − TS We ﬁnd that dG = dU + P dV + V dP − T dS − SdT = V dP − SdT + µdN (6.17) We can see that the chemical potential. so the chemical potential is an intensive quantity. We can see that the number of particles N is also extensive. THE GRAND CANONICAL ENSEMBLE The chemical potential µ is the amount of energy by which the system changes when you add a single particle to the system while keeping the entropy and volume constant. µ) = U − T S − µN dΦ = dU − T dS − SdT − µdN − N dµ (6.20) . that is when the system parameters all double.µ. then either the Gibbs free energy or the number of particles must not be extensive.13) It follows that the Gibbs free energy is a function of the temperature. pressure and number of particles of the system.16) T.2 The Grand Free Energy Φ ≡ Φ(T. the value of the Gibbs free energy also doubles.70 CHAPTER 6. are intensive quantities.14) (6. This gives an alternative meaning to the chemical potential.P The Gibbs free energy is an extensive function. the relationship between the Gibbs free energy and the number of particles must be a linear one. else the Gibbs free energy would ∂G not be extensive. because if it wasn’t. it is the Gibbs free energy per particle in the system.18) (6. The chemical potential. in terms of the Gibbs free energy is µ= ∂G ∂N (6. but they are. and since ∂N T.

so Φ = −P V (6.3: A system in thermal and diﬀusive equilibrium with a resevoir Let s1 and s2 be two possible microstates of the system and P (s1 ) and P (s2 ) the respective probabilities of the system plus resevoir.21) V.NR.T.6. THE GRAND CANONICAL ENSEMBLE: THE GIBBS FACTOR This gives us the following relationships between thermodynamic quantities and the grand free energy S P N = = = − − − ∂Φ ∂T ∂Φ ∂V ∂Φ ∂µ 71 (6.3. By the fundamental assumption of statistical mechanics P (s1 ) is proportional to the multiplicity of the microstates of the resevoir.22) T.25) . Resevoir VR .V We can arrive at a simpler deﬁnition of the grand free energy by substituting it into the deﬁnition of the Gibbs free energy G = U − TS + PV = Φ + µN + P V but we know that G = µN . The ratio of the two probabilities is gR (s1 ) e kB P (s1 ) = = SR (s2 ) P (s2 ) gR (s2 ) e kB SR (s1 ) (6.23) T.M N Figure 6.24) 6.µ (6.3 The Grand Canonical Ensemble: The Gibbs Factor Consider a system in thermal and diﬀusive equilibrium with a much larger system which acts as a resevoir. and likewise so is P (s2 ).µ (6.

The internal energy of a system is given by U (T. µ) = s ε(s)P (s) (6.72 CHAPTER 6. THE GRAND CANONICAL ENSEMBLE Where SR (s1 ) is the entropy of the resevoir when the system is in state s1 .27) We can now write the ratio of probabilities as kB T P (s1 ) e = −(ε(s2 )−µN (s2 )) P (s2 ) kB T e −(ε−µN ) −(ε(s1 )−µN (s1 )) (6. Using the Gibbs factor for the probilities we get U = = = 1 Z 1 Z ε(s)e s −(ε(s)−µN (s)) kB T ∂ Z + µN ∂β ∂ µ ∂ − + ln Z ∂β β ∂µ − (6. This simpliﬁes to SR (s1 )−SR (s2 ) P (s1 ) kB =e P (s2 ) (6. and like the Boltzmann factor. needed to normalize the Gibbs factor to a probability is the sum of the Gibbs factors for all states of the system.26) Since the resevoir is so much larger than the system the transition from state s1 to s2 can be viewed as an inﬁtesimal process. We can use a similar method to . Z= e s −(ε(s)−µN (s)) kB T (6.28) 1 (dUR − µdNR ) T (6.31) where P (s) is the probability of the system being in state s. the constant. the probability of the system being in a state with energy ε is proportional to the Gibbs factor. Similarly. V.32) Where Z is the ordinary partition function. This means dSR = and since the volume is ﬁxed SR (s1 ) − SR (s2 ) = −1 [ε(s1 ) − ε(s2 ) − µN (s1 ) + µN (s2 )] T (6.29) e kB T is called the Gibbs factor. Z.30) Z is called the Grand Partition function of the Gibbs’ sum.

µ) = −kB T ln Z(T. we consider Eqn 6. V ) is the constant of integration and is independent of µ.34) T.V Integrating both sides with repsect to µ gives Φ = −kB T ln Z(T. V.36) But for µ = 0. V. V. µ = 0) + Q(T.39) µ. This means Q(T. µ) (6. µ) kB T ∂µ (6.V P = kB T (6.21 and 6.40) T.4. V. Hence Φ(T.6. the grand free energy reduces to the Helmholtz free energy and the grand canonical ensemble reduces to the canonical ensemble.37) But we know that the Helmholtz free energy is given by F = −kB T ln Z.µ . To determine the value of Q. µ) = s N (s)P (s) 1 Z N (s)e s −(ε(s)−µN (s)) kB T = = = ∂Z 1 kB T Z ∂µ ∂ ln Z(T. µ) + Q(T.V ∂ ln Z ∂µ (6.35) Q(T. V ) (6. µ = 0) = −kB T ln Z(T.22 we ﬁnd that in terms of the grand partition function the entropy and pressure of a system are S = kB ∂ T ln Z ∂T ∂ ln Z ∂V (6.4 Relation of Grand Partition Function to Grand Free Energy We now have a deﬁnition of the average number of particles in terms of both the grand free energy and the grand partition function.35 at µ = 0 Φ(T.33) 6. V. V ) must be zero. V. RELATION OF GRAND PARTITION FUNCTION TO GRAND FREE ENERGY73 calculate the average number of particles in the system N (T.38) By substituting this deﬁnition of Φ into Eqns 6. V. V ) (6. V ) (6. Making these substitions we get F = −kB T ln Z + Q(T. Equating these deﬁnitions we get N =− ∂Φ ∂µ = kB T T.

74 CHAPTER 6. THE GRAND CANONICAL ENSEMBLE .

5 Consider a system of two indistinguishable particles in one dimension. Chapter 6 7. The wave function of the system can be written Ψ(x1 . Section 7.1 Indistinguishable Particles in Quantum Mechanics Ref: Schroeder. x2 ). The probability of ﬁnding one particle at x1 and a second at x2 is proportional 2 to |Ψ(x1 .2 Kittel and Kroener.Chapter 7 Quantum Statistics Key Concepts • Indistinguishable particles in quantum mechanics • Fermions and bosons • Spin-statistics theorem • Bose-Einstein statistics • Fermi-Dirac statistics • Fermi-Dirac distribution function • Bose-Einstein distribution function • Relation to Boltzmann statistics Reading Schroeder. Appendix A. x2 )| 75 .

swapping the position of the particles doesn’t change anything. . .76 CHAPTER 7. .1. They obey the Fermi-Dirac statistics. This implies Ψ(x1 . protons. . helium-4 atoms They obey the Bose-Einstein statistics. x2 ) = Ψa (x1 )Ψa (x2 ) i. x1 )| 2 2 A factor of eiθ (instead of ±) is not allowed. because if we interchange the particles twice then we need to get back our original wave function. Then the wave function for the two particles is given by Ψ(x1 . |Ψ(x1 . that is. xN ) Note also that for particles with spin. xs . QUANTUM STATISTICS However. helium-3 atoms. . neutrons. this probability cannot depend on the order of x1 and x2 in the wave function. The negative case Ψ(x1 . because the particles are indistinguishable. S2 ) = Φa (x1 )Φa (x2 )( √ )(δs1 ↑ δs2 ↓ − δs1 ↓ δs2 ↑ ) 2 7. x2 ) = Ψ(x2 . . the wave function of the system must be unchanged under the exchange of any two arguments. x2 . . The above considerations are also valid for a system of N distinguishable particles. . The positive case Ψ(x1 . S1 . x1 ) corresponds to bosons. that is Ψ(x1 . .e. . . Suppose both particles are in the same quantum state. This is the Pauli exclusion principle. For bosons. . xs . and the wave function is symmetric. . . . x2 . . x1 ) = Ψ(x2 . x1 ) corresponds to fermions and the wave function is antisymmetric. the wave function will not just depend on spatial co-ordinates. described by a wave function Ψa (x). xr . pions. All co-ordinates must be exchanged (spin and space).1 Bosons and Fermions Bosons are particles which have the property that more than one particle can occupy the same quantum state. x2 )| = |Ψ(x2 . x2 ) = ±Ψ(x2 . Examples: photons. xr . but also the spin quantum numbers. . . . xN ) = Ψ(x1 . . . . Examples: electrons. Fermions are particles with the property that two identical fermions can not occupy the same quantum state (the Pauli exclusion principle). for example 1 Ψ(x1 . x2 . x1 ) So this implies that the wave function is symmetric. and hence can only happen for bosons: Two fermions cannot occupy the same quantum state. so for a fermion system the spatial part of the wave function could be symmetric and the spin part antisymmetric. x2 ) = −Ψ(x2 . . . .

Particles with half-integer spin are fermions. If this is the case. Quantum statistics only become important in dense systems where there is a reasonable chance that two or more particles might occupt the same quantum state.1) for N identical non-interacting particles breaks down. must be an integer. there are 25 states accessible to the system. The allowed system states for Fermions are 11000 01010 10100 01001 10010 00110 10001 00101 01100 00011 so there are a total of 10 allowed states: ZF = 10. If the particles are distinguishable. .2. Z= s e−βEs = s = number of states so the partition function is just the number of states accessible to the system.1 predicts that Z = 1 · 25 = 12. then the expansion Z= 1 N Z N! 1 (7. the following additional states are permitted: 20000 02000 00200 00020 00002 . the partition function will be Z = 5 × 5 = 25. 7.e.2. h angular momentum in units of 2π ) are bosons.1. Suppose there are 2 particles which can occupy these states.2 Quantum Statistics This is the most important application of the Gibbs factor. . QUANTUM STATISTICS 77 The Spin-statistics Theorem: Particles with integer spin (0. because the counting factor N ! assumes the paticles are always in diﬀerent states. because Z. that is. i. Example. For Bosons. being the number of states.7. Consider a model with 5 single particle states. This theorem is a deep consequence of relativity and quantum ﬁeld theory. and all states are equally accessible. Because Es = 0 ∀ s.. For indistinguishable particles.5 2 But this is impossible. It was ﬁrst proven by Pauli in 1950. all with zero energy. Equation 7.

the average distance d between particles must be much greater than λT . The N ! factor fails for Fermions because it tries to include the cases where the two particles are in the same state. this can only happen one way. so it underestimates. If Z1 N then quantum statistics is not important. It fails for bosons. d ∼ 3nm and λT < 0. Examples include: • Liquid helium • Electrons in a metal • Neutron stars • Photons in an “oven” • Atoms in a “trap” Such systems are referred to as quantum gases or quantum liquids. which isn’t allowed for fermions. QUANTUM STATISTICS so that ZB = 15. because there are many more states than particles. Given temperature and pressure. but when the particles are in the same state. the particle density V /N can be computed from P V = N kB T . . The condition Z1 N then becomes V N vQ = λ3 T (7. Z1 = s1 e−β (s1 ) = the number of available single particle states.78 CHAPTER 7.1: Normal vs Quantum Gas Quantum statistics become important at “high” densities and “low” temperatures.02nm Figure 7.3) or equivalently. V For the monotonic ideal gas.2) where λT is the thermal de Broglie wave length. ∼ In general. For air at room temperature. because it assumes that each possible arrangement occurs twice (in this case). and so the chances of two particles being in one state is low. Z1 = vQ where vQ is the quantum volume discussed previously: 3 vQ ≡ λT = h √ 2πmkB T 3 (7.

For − µ << kB T .4) where Z is the grand partition function. which is in equilibrium with a system at temperature T and chemical potential µ. at low energy levels.5) The distribution for various temperatures is shown in Figure 7. the sum over all states and all number of particles. nF D ( ) → 0 . which is given by n = n n · P (n) = 0 · P (0) + 1 · P (1) = P (1) e−( −µ)/kB T 1 + e−( −µ)/kB T 1 = ( −µ)/kB T + 1 e ∼ = nF D ( ) = This is called the Fermi-Dirac distribution nF D = 1 e( −µ)/kB T +1 (7.3.2.Fermions Because two fermions cannot occupy the same quantum state.7. (7.3.3 Distribution Functions We ﬁrst focus on a system consisting of just one single particle state.1 Case I . i. Therefore.e. DISTRIBUTION FUNCTIONS 79 7. is just a sum over the number of particles. depending on the number of particles in that state. E(n) = n because every particle must go into the 7. nF D ( ) → 1 At high energy levels. What we’re considering now is one energy level which can be in many diﬀerent “states”. n can only be 0 or 1. The probability of the state being occupied by n fermions is P (n) = = = 1 exp(−(E(n) − µn)/(kB T )) Z 1 exp(−(n − µn)/(kB T )) Z 1 exp(−n( − µ)/(kb T )) Z energy state. meaning − µ >> kB T. Hence Z = 1 + exp(−( − µ)/(kB T )) Occupancy of the state is deﬁned to be the average number of particles.

Bosons Here. where x = e−( −µ)/kB T n=0 = = 1 1−x 1 − e−( 1 −µ)/kB T The series only converges if x < 1. Z = = ∞ n=0 exp(−n( − µ)/kB T )) xn . QUANTUM STATISTICS I nFD(ε) T=0 ~K BT high T low T ε 0 µ Figure 7.2: Fermi-Dirac Distribution 7. ne Z n=0 1 ∂Z Z ∂y = − Since Z = 1 1−e−y . The occupancy of the state is ∞ n=0 ∞ n = = n · P (n) where y = −µ kB T 1 −ny . i. any number of particles can be in the state.3. so the chemical potential of a system of bosons is always less than the lowest energy level.2 Case II .80 CHAPTER 7.e. . µ < .

3 Comparison with Boltzmann Statistics Let’s compare these distributions with the Boltzmann distribution which describes distinguishable particles.3 nBE = 1 exp −µ kB T 1 ∂ ∂y 1 − e− y −e−y = −(1 − e−y ) × (1 − e−y )2 e−y = 1 − e−y 1 = ey − 1 = −(1 − e−y ) (7. DISTRIBUTION FUNCTIONS 81 n Thus we have the Bose-Einstein distribution function shown in Figure 7.3: Bose-Einstein Distribution Function 7. In this case.6) −1 n µ µ+kBT ε Figure 7.3.3.7. the probability of a particle being in a state with energy is P( ) = 1 exp(− ) Z1 kB T .

QUANTUM STATISTICS straight from the partition function.7) Z1 We however want the probability without referring to the total number of particles. consider an idea gas of N non-interacting indistinguishable particles: 1 N Z= Z N! 1 The Helmoltz-Free energy is given by F = −kB T ln Z = −kB T (N ln Z1 − ln N !) = = −kB T (N ln Z1 − N ln N + N ) −kB T N (ln Z1 + 1 − lnN ) Then the chemical potential µ is given by µ = ∂F ∂N T.7 becomes −µ)/kB T (7.N = −kB T (ln Z1 + 1 − ln N ) + kB T N ( = Therefore So our expression for nBoltzmann −kB T ln( Z1 ) N 1 ) N Z1 − µ = e kB T N in Equation 7. Hence we see that when − µ is suﬃciently large so that e( nF D ( ) ≈ nBE ( ) ≈ nBoltzmann ( ) −µ)/kB T >> 1. . To eliminate N . Notice that for the Bose-Einstein distribution there is no limit to the number of particles that can occupy the ground state.10) (7.9) −µ)/kB T +1 (7.12) −µ)/kB T 1 e( −µ)/kB T e( −1 1 nBoltzmann ( ) = Figure 7. If there are N particles the average number of particles in this state is N −k T e B nBoltzmann ( ) = N P ( ) = (7.11) (7.8) nBoltzmann ( ) = e−( The three distribution functions are thus nF D ( ) = nBE ( ) = 1 e( (7. then The ±1 factor in the numerator of the Bose-Einstein and Fermi-Dirac distributions is a result of the particles being indistinguishable in quantum mechanics.82 CHAPTER 7.4 shows the three distributions.

4: Comparison of the Fermi-Dirac. . When ( − µ)/kB T >> 1.7. all for the same value of µ.3. Bose-Einstein and Boltzmann distributions. the three distributions become equal. DISTRIBUTION FUNCTIONS 83 n Boltzmann Bose−Einstein 1 Fermi−Dirac µ µ+kBT ε Figure 7.

Chapter 7 7. As a frst step.84 CHAPTER 7. we take T = 0. it makes sense because at absolute zero we expect all particles to be in their lowest possible states. we can’t have more than one Fermion per state (two if we . Examples of a Fermi Gas: • Conduction (free) electrons in a metal • Liquid 3 He • Neutrons in a neutron star • Electrons in a white dwarf star • protons and neutrons in an atomic nucleus We assume the temperature is suﬃciently low that vQ = h √ 2πmkB T 3 >> V N This is the opposite condition to that required for the validity of Boltzmann statistics. QUANTUM STATISTICS 7.1 What is a Degenerate Fermi Gas? A degenerate Fermi gas is a system of fermions where quantum statistics has a signiﬁcant eﬀect on the macroscopic propreties of the system. and all with > µ are unoccupied – mathematically. we are considering the case where the atoms are packed very closely together so that quantum statistics does become important. Section 7.2 Zero Temperature All single particle states with < µ are occupied. we obtain this by letting T → 0 in the Fermi-Dirac distribution. Here.4.3 Kittel & Kroener.4 Degenerate Fermi Gas Key Concepts • Examples • Fermi energy • Fermi temperature • Degeneracy condition (T << TF ) Reading Schroeder. 7.4. But because we are looking at Fermions. Physically.

so the energy of the system goes up by ∆U = F . the more states are needed to place them all. which we will show in a moment. The fermi energy gives the cut oﬀ energy for the distribution.15) At T = 0. and so the higher the fermi energy.5: Fermi-Dirac Distribution at T = 0 consider spin).V (7.7.14) S. We ﬁrst ﬁnd the allowed energy levels. DEGENERATE FERMI GAS 85 nFD(ε) I 0 µ=εF ε Figure 7. because that’s the next available level. if we add one particle (∆N = 1) then it must go in with an energy F . We now calculate F for a system of N free electrons conﬁned to a cube of volume V = L3 . Thus ∆U µ(T = 0) = = F ∆N The fermi energy is determined by the total number of particles in the system – the more particles. The fermi energy is deﬁned by F = µ(T = 0) (7. . Therefore the particles ﬁll up all the lowest energy states in order.13) Note: The fermi energy varies with temperature. We can see that the above deﬁnition makes sense because µ = ≈ ∂U ∂N ∆U ∆N (7.4.

The number of states with energy less than F is the volume of a sphere with corresponding radius nmax given by h2 n2 F = 8mL2 max (See Figure 7. a constant energy surface is a sphere. the allowed wavelengths and corresponding momenta are hn 2L h pn = λn = = n λn 2L and this extends to the three components of momentum in three dimensions. In three dimensions.16) In “n-space”.86 CHAPTER 7. the allowed energyies are (p) = = = p2 2m 1 2 (p + p2 + p2 ) y z 2m x 2 h (n2 + n2 + n2 ) y z 8mL2 x (7.6) . QUANTUM STATISTICS For a one dimensional box.

4.6: n-space . DEGENERATE FERMI GAS 87 Figure 7.7.

This is equivalent to kB T << F (7. most metals at room temperature are highly degenerate. QUANTUM STATISTICS Because all particles have energy less than F by deﬁnition.88 CHAPTER 7. n = N ≈ 1022 − 1023 cm−3 . meaning it is intensive – if we V double the size of the system.17) where we have taken spin into account.18) (7. with F ≈ 1 − 10eV. F does not change.19) Note that F only depends on the density N .22) In a typical metal. TF ≈ 104 − 105 K. N = 2 × volume of 1 4 = 2 · · πn3 8 3 max π 3 n = 3 max 1 8 sphere (7. Thus. V We now reconsider the requirement for degeneracy N << vQ . In typical V elemental metals. and it is often suﬃcient to consider them (for degeneracy purposes) to be at T = 0! . this must be N . and so we can ﬁnd nmax and hence F in terms of N .21) so that the degeneracy condition becomes T << TF (7.20) We can also deﬁne the fermi temperature by TF = F kB (7. The fermi energy is then F = = h2 n2 8mL2 max h2 8mL2 3N πV 2 3 (7.

DEGENERATE FERMI GAS 89 Table 7.4.7.1: Photocopy – Fermi temperatures table .

ny . When the particles are degenerate (or close to it) they resist being pushed closer together. which prevents two fermions being in the same state.nz (n) d3 n (n) nmax (7. PV = 2 N kB T F 5 (7.4. (7.4 Degeneracy Pressure The fermi gas has pressure even at T = 0: P = = = − ∂U ∂V S.90 CHAPTER 7.4. U = 2 nx .25) This pressure is due to the exclusion principle. since the particles have all 2 energies between 0 and F .N ∂ − ∂V 2N F 5V 3 h2 N 5 8m 3N π 2 3 V −3 2 Thus. QUANTUM STATISTICS 7.24) So the average energy per particle is 7. .3 Internal Energy at Zero Temperature We can now calculate the internal energy per particle of a fermi gas.23) = 2 = 2 0 nmax dn · n 2 0 π 2 sin θdθ 0 π 2 dφ (n) = = = = π 0 (n)n2 dn nmax πh2 n4 dn 2 8mL 0 πh2 5 n 40mL2 max 3 N F 5 3 5 F. We would expect that it would be approximately 1 F .

3 99.4. the compressibility of metals is dominated by that due to the degeneracy pressure of the electrons.5 228 Measured B 11.27) Compare this to an ideal gas where B = P = N kB T (check this!).7. The free electron value is that for a free electron gas at the observed density of the metal 7. meaning less compressible. DEGENERATE FERMI GAS Metal Li Na K Rb Cs Cu Ag Al Free electron B 23. and while the crystal of ions is hard to compress. P = ∼ = So then. B = −V For a fermi gas.92 1. Mathematically.19 2.43 134. Electrons in V a (room temperature) metal have a much higher bulk modulus (because usually TF >> T ). B= 2 F N 5 V 2 V −3 V 5 V −3 ∂P ∂V (7. than an ideal gas of similar density.5 6.28 1.2: Bulk Moduli in 101 0 dynes/cm2 for some typical metals.9 76.23 3.0 91 Table 7.54 63.26) T 2 5 2N F P = N = kB TF 3 3 V 3V (7. Metals are composed of ions and electrons.5 Bulk Modulus The bulk modulus is the change in pressure over the fractional change in volume – a high bulk modulus means the material is diﬃcult to compress. while an easily compressible material has a small B.9 9.42 2.81 1.8 34. .4.

7 Ashcroft & Mermin.5. 661 . p. Ch. Ch. Solid State Physics.92 CHAPTER 7.1 Reading Schroeder. Section 7.3 Kittel & Kroener. 2. QUANTUM STATISTICS 7.5 Degenerate Fermi Gases at Low Temperatures Key Concepts • T << TF . but > 0 • Density of states • Temperature dependence of chemical potential µ(T ) • Sommerfeld expansion • Heat capacity CV (T ) ∼ γT • Pauli paramagnetism • heavy fermions 7.

DEGENERATE FERMI GASES AT LOW TEMPERATURES 93 Figure 7.5.7.7: Photocopy – Fermi-Dirac Distribution at Low Temperatures .

5.94 CHAPTER 7. Thus we expect the internal energy at low temperatures to be U (T ) = U (T = 0) + aN kB T F kB T where a is a number of order one. The heat capacity at low temperatures will then be CV (T ) = ∂U ∂T =a V 2 N kB F T which is consistentwith the third law of thermodynamics. I nFD(ε) T=0 KBT 0 εF ε Figure 7.2 Small Non-Zero Temperatures We now consider the case 0 < T << kF = TF .5. The density of states. QUANTUM STATISTICS 7. Recall that the Fermi-Dirac distribution function looks like Figure 7. If we let N (E) be the total number of single particle states with energy less than E then E N (E) = −∞ d · g( ) . This applies to metals at room B temperature. denoted g( ) is the number of single particle states per unit energy – the number of states “near” energy .8.7. 7. of order N kB T have kinetic energy kB T F greater than F .3 Density of States This is an important concept with very wide-ranging applications. also see Figure 7. for instance.8: Fermi-Dirac Distribution at Low Temperatures Now a fraction of the electrons.

If { α }α denotes all the single-particle energy states. DEGENERATE FERMI GASES AT LOW TEMPERATURES It follows that dN (E) .29) where δ(x) is the Dirac delta function. dE that is.7. of energy levels with Θ( F α − α) ≤ F = −∞ g( ) d (7.5.32) .31) The total energy at T = 0 is U (T = 0) = α F α Θ( F − α) = −∞ d g( ) (7. For a system of N fermions at T = 0. deﬁned such that δ(x) = 1 for x = 0 0 otherwise but with the special property that the function is normalised to 1: ∞ −∞ dx δ(x) = 1 It is also the derivative of the step function Θ(x) which is deﬁned to be Θ(x ≥ 0) = 1 It folows that E Θ(x < 0) = 0 N (E) = −∞ E d g( ) d −∞ E α = = α δ( − α) −∞ d δ( − α) α) = α Θ(E − (7. consistent with the original deﬁnition.28) δ( − α) (7. F is deﬁned by N = = α F no.30) which the the total number of states with energy less than E. we can also write g(E) = g( ) = α 95 (7. the number of states between E and E + dE is g(E) dE.

N = N . of states with energy < E 1 = volume of the sphere in n-space 8 1 4 3 = · πn 8 3 0 p2 2m h2 (n2 + n2 + n2 ) z y 8mL2 x h where E = 8mL2 n2 .33) U (T ) = α α nF D ( α ) ∞ −∞ = d g( )nF D ( ) (7. Here we are considering particles with no spin. ny . 0 This is similar to what we did for the T = 0 case. QUANTUM STATISTICS The above expressions generalise naturally to ﬁnite temperature: N (T ) = α nF D ( α ) ∞ −∞ = d g( )nF D ( ) (7. . adding the number of states with each energy times the (average) number of particles in each of those states state. Then N (E) = total no. The Fermi-Dirac distribution at T = 0 is a backwards step function with the jump down at F .e. and so the general expressions above are consistent with the zero temperature limit.96 CHAPTER 7. to ﬁnd N . i. .34) In words. 7. we showed that the allowed values of the energy of a single state particle (fermion or boson) are (p) = = for nx . Previously. . 2.5. 1. 2 . subject to the boundary condition that the wave function vanishes on the surface of the cube. except that we’re no longer saying that all these states are ﬁlled. nz = 0. we sum over all energies.4 Density of States in a Three Dimensional Cube Method 1 We now ﬁnd the density of states for a fermi gas conﬁned to a three dimensional cube.

ny . Here.5.39) dn n2 δ 0 − h2 |n|2 8mL2 When working with this deﬁnition of the density of states. the next step is to make a substituion of x for .). and α ≡ (n) = h2 2 (n2 |n2 + nz ) 8mL2 x y We convert the sum to an integral (in polar co-ordinates) and if the energy spacings are small. h2 |n|2 8mL2 π 2 g( ) = α δ ∞ 0 − 2 (7. because there are twice as 2 many states.5.5 Density of States in a Three Dimensional Cube Method 2 Let’s repeat the derivation using the deﬁnition g( ) = α δ( − α) where the sum in this case is over all (nx . in δ( − . this is a good approximation. g(E) = 7. DEGENERATE FERMI GASES AT LOW TEMPERATURES We thus have N (E) = = And so 2 π 8mL2 E 6 h2 3 3 π √ L3 · 8 8 3 · E 2 m2 6 h 3 97 (7. .35) √ L3 3 √ dN (E) (7. this means we set x= so n= n2 dn = h2 n2 8mL2 8m L√ x h 3 √ √ 8m L h x· 1 dx √ 2 x .36) = 2π 8 2 m 2 E dE h For fermions with spin.1 we multiply this by 2.7. . . .38) (7.37) π 2 = = π 2 dn n ∞ sin θ dθ 0 dφδ 0 − h2 |n|2 8mL2 (7. nz ).

note that nF D has some symmetry about = µ. as the temperature increases.40 determines µ as a function of temperature – as T increases. Therefore.98 Thus. µ decreases slightly. Let’s consider ﬁrst a constant density of states g( ) ≡ g. g( ) = = CHAPTER 7. reducing the overall size. We also deﬁne g( ≤ 0) = 0 – there are no states with energy less than zero in this case. so that the peak of nF D moves to the left. and increases with . and so the area is indeed still N. however.33. 7. To see why. then Equation 7.9: Constant Density of States If the number of particles in the system is conserved. etc. and it would appear the number of particles has increased! This problem is resolved if. Now. QUANTUM STATISTICS 3 π √ L 8m 4 h 3 3 L √ π (8m) 2 3 4 h ∞ 0 √ dx xδ( − x) which with some slight re-arranging agrees with the previous result. Now.40) If N is ﬁxed. .5. consider the case where the density of states is not constant. in the sense that the probability of a state at energy µ + δ being occupied is the same as the probability of a state at µ − δ being unoccupied. due to the higher density of states on the right. µ must decrease.10. Such states can correspond to bound states like potential wells. the area under the graph to the right of µ will be scaled more than the “empty” area above the line to the left. we said before that N = = d g( )nF D ( ) d g( ) 1 e( −µ)/kB T +1 (7. and Figure 7. (See Tutorial ***) The total number of particle in the system is determined by Equation 7. the area of the graph is greater than N . the two hatched areas must be equal. the area should still be N . and isn’t scaled as much by g( ). Figure 7. as shown in Figure 7. then at non-zero temperatures.11. Because of the symmetry of nF D about µ.6 Temperature Dependence of the Chemical Potential ∞ −∞ ∞ −∞ For a general density of states g( ).

10: Non-constant Density of States Figure 7.5. DEGENERATE FERMI GASES AT LOW TEMPERATURES 99 g (E) g (E) g(E)nFD(E) area = N area = N ε ε εF= µ (T = 0) εF= µ (T = 0) Figure 7.11: Photocopy – Temperature dependence of µ (photocopy) .7.

5. Also. as → +∞.41 from N= ∞ −∞ dx N (µ + xkB T ) (ex ex + 1)2 .41) d g( )nF D ( ) N = N ( )nF D ( ) − ∞ −∞ d N( ) dnF D ( ) d As → −∞.7 The Sommerfeld Expansion F We now ﬁnd explicitely µ(T ) when T << From ∞ N= we ﬁrst integrate by parts: −∞ ∞ −∞ = µ(T = 0) (7. N ( ) → 0 and nF D ( ) → 1. so the boundary term is zero. For T << F . − dnF D is sharply peaked at = µ d Figure 7. (7.12: Sharp peak in − dnF D d We can see this mathematically by − dnF D d = = − 1 d d e( −µ)/kB T + 1 ex 1 kB T (ex + 1)2 to x.42) where x = k−µ BT We now change our integration variables in Equation 7.100 CHAPTER 7. QUANTUM STATISTICS 7. nF D ( ) → 0.

.44) √ so g ( F) g( F ) = and so we do have an expansion on powers of . . 1 N (µ + xkB T ) = N (µ) + N (µ)xkB T + N (µ)(xkB T )2 + . Thus. . N (µ) = e dN ( ) d =µ ∞ 101 = g( = µ) so that N = N (µ)I0 + kB T g(µ) where In I0 I1 I2 1 I1 + (kB T )2 g (µ)I2 2 −∞ ex (ex + 1)2 −∞ ∞ d 1 = dx − =1 x+1 dx e −∞ = 0. we must have a= and so to second order in kB T F π 2 g( 6 g( F) F) .43) Now. (remembering that F ≡ µ(T = 0)) and substitute in this expression and work consistently to second order in T : N = N( F) − a(kB T )2 g( F) + π2 g( 6 F )(kB T ) 2 But by deﬁnition of the fermi energy. 6 (7. since the integral is antisymmetric about x = 0 2 π = (See Appendix B5 in Schroeder) 3 = dx xn ∞ Thus. . This is reasonable. we ﬁnd that N = N (µ) + π2 g (µ)(kB T )2 + . . because the total number of states varies slowly on the energy scale of kB T when T is small.5.7. g(e) ∼ kB T F − π2 g ( F ) (kB T )2 6 g( F ) 1 2 F (7. N ( F ) = N – there must be enough states with energy less than F to place all the particles. we let µ(T ) = F − a(kB T )2 + . 2 However. by deﬁnition. DEGENERATE FERMI GASES AT LOW TEMPERATURES We perform a Taylor expansion of N ( ) about = µ. . F µ(T ) = For a 3d system.

we previously showed that µ(T ) = Taylor expand h(µ) around F . 6 F Then.102 CHAPTER 7.8 Heat Capacity ∞ −∞ We now evaluate the internal energy U (T ) = d g( )nF D ( ) for kB T << F . because nF D ( ) → 0 as → ∞ and h( ) → 0 as term is zero. . giving h(µ) = h( From the deﬁnition of h( ). QUANTUM STATISTICS 7. The calculation is similar in spirit to that for ﬁnding µ(T ). h( h ( = ) = F F) F F) − π2 g ( F ) 2 6 g( F ) (kB T ) . 2 and substituting this into the integral gives U (T ) = h(µ) + π2 (kB T )2 h (µ) + . . . . the boundary dx h(µ + xkB T ) ex (ex + 1)2 We can expand h as a Taylor series 1 h(µ + xkB T ) = h(µ) + xkB T h (µ) + (xkB T )2 h (µ) + .47) h( )nF D ( )|−∞ − d h( ) d nF D ( ) d Again. so we can −h( F) π2 g ( F ) (kB T )2 6 g( F ) g( g( F ) F) + F g ( F) .46) (7.45) (7. Let h( ) be deﬁned by h( ) = −∞ dE [E g(E)] Note that h( F ) = U (T = 0) Integrating U (T ) by parts gives U (T ) = = = ∞ −∞ ∞ −∞ d ( g( )) nF D ( ) d d d dE [Eg(E)] nF D ( ) −∞ ∞ ∞ −∞ (7. Proceeding as before. U (T ) = ∞ −∞ → −∞.5.

9 Low Temperature Heat Capacity of Metals CV (T ) = γT ↑ electrons + βT 3 ↑ phonons Plotting CV (T ) versus T 2 T should be a straight line with gradient β and intercept at T = 0 of γ. DEGENERATE FERMI GASES AT LOW TEMPERATURES Collecting terms. .7. Note that for ﬁxed density. We can also write m g( F ) = kF ( π)2 where kF is the fermi wave number.48) (7. g( F ) scales with m.5. If g( F ) is larger than for the free (non-interacting) electron model.50) h2 = 8m 3N πV 2 3 and the density of states per unit volume is 3√ π g( F ) = 3 (8m) 2 F 2h which can be rewritten in terms of the fermi energy as g( F) = 3N/V 2 F Notice that g( F ) is completely determined by the conduction electron density N/V .49) π2 2 g( F )kB 3 For non-interacting electrons in three dimensions. the fermi energy is γ= F (7. we have π2 π2 2 (g( F g ( F )(kB T ) + 6 6 The second and fourth terms cancel exactly. we say the electrons have an eﬀective mass given by γ m∗ = me obs γfree 7.5. leaving U (T ) = U (T = 0) − U (T ) − U (T = 0) = It then follows immediately that CV (T ) = where ∂U ∂T = γT V F) 103 + Fg ( F )) (kB T ) 2 π2 g( 6 2 F )(kB T ) (7.

104

CHAPTER 7. QUANTUM STATISTICS

Figure 7.13: Photocopy – Experimental Heat Capacity Data

Table 7.3: Photocopy – Experimental values of experimental heat capacity

7.6. MAGNETIC SUSCEPTIBILITY OF METALS – PAULI PARAMAGNETISM105

7.6

**Magnetic Susceptibility of Metals – Pauli Paramagnetism
**

= = − µB B + µB B

**In a magnetic ﬁeld B, the energy of the electrons becomes
**

↑ ↓

due to Zeeman splitting, where is the energy in the absence of a magnetic ﬁeld. If we neglect the orbital motion of the electron the density of states is g↑ ( ) g↑ ( ) = = 1 g( − µB B) 2 1 g( + µB B) 2 (7.51) (7.52)

that is the density of states of the spin up electrons (for example) is half the density states in no magnetic ﬁeld, at an energy µB B less than . The total number density of electrons of spin σ =↑, ↓ is nσ = where nF D ( ) = eβ( d gσ ( )nF D ( ) 1

−µ)

(7.53)

+1

**The chemical potential µ(T ) is determined by n = n↑ + n ↓ where nσ = g( ) vaires on an energy scale of ∼ approximation we have gσ ( ) = = and therefore g↑ ( ) + g↓ ( ) = = 1 1 g( ) + µB Bg ( ) + 2 2 g( ) 1 1 g( ) − µB Bg ( ) 2 2 d gσ ( )nF D ( )
**

F

so since µB B <<

F,

to a good

1 g( ± µB B) 2 1 1 g( ) ± µB Bg ( ) 2 2

106 Thus, n = = = n↑ + n↓

CHAPTER 7. QUANTUM STATISTICS

d g↑ ( )nF D ( ) + d g( )nF D ( )

d g↓ ( )nF D ( ) (7.54)

which is the same as the zero-ﬁeld equation. Hence, from Equation 7.44, we have µ(T ) = The magnetisation is M = −µB (n↑ − n↓ )

∞ −∞ ∞ =∞ F

1+O

kB T

F

2

= −µB = µ2 B B

d nF D ( ) [g↑ ( ) − g↓ ( )] d nF D g ( ) → 0 and

**Integrating by parts, and using the fact that nF D ( ) → 0 as g( ) → 0 for ≤ 0
**

2 M = µB B ∞ −∞

d g( ) −

∂nF D ( ) ∂ =

F

For T << in

T

F

F

2

∼µ =

∞ −∞

∂nF D ( ∂

) is sharply peaked at

and so to leading order

d g( ) −

∂nF D ∂

= =

g( g(

F) F)

∞ −∞

d

−

∂nF D ∂

(7.55) (7.56)

**The magnetic susceptibility χ is given by χ= Working to second order in
**

kB T

F

M = µ2 g( B B

F)

we ﬁnd

F)

χ(T ) = µ2 g( B

1−

π2 12

kB T

F

2

(7.57)

Note that this weak temperature dependence is in contrast to that for isolated spin- 1 particles which obey Curies law 2 χ(T ) ∼ 1 T

15: Photocopy – Temperature dependence of magnetic susceptibility of 3 He Figure 7.6.7.16: Photocopy – Temperature dependence of heat capacity of 3 He .14: Photocopy – Temperature dependence of χ Table 7.4: Photocopy – Comparison of free electron and measured Pauli susceptibilities Figure 7. MAGNETIC SUSCEPTIBILITY OF METALS – PAULI PARAMAGNETISM107 Figure 7.

QUANTUM STATISTICS 7. .1 Heavy Fermion Metals • interaction between neighboring electrons so strong that electrons cannot be considered separately • UPt3 . LiV2 O4 . . CeCu2 Si2 .108 CHAPTER 7. UBe1 3. • discovered in late 70’s • some are superconductors γ ∼ 1J/molK 2 m∗ ≈ 100 − 1000 me χe (T ) is also enhanced by a factor of 100-1000 compared to elemental metals.6. . .

1) 2 8mL 8mL2 At very low temperatures it is possible to ﬁnd a macroscopic number N0 of the N bosons are still in the ground state. The value of N0 is given by the Bose-Einstein distribution function 1 N0 = ε0 −µ (8.1 Macroscopic Occupation of the Ground State Consider N atomic bosons of mass m conﬁned to a volume V = L3 .2) e kB T − 1 ε0 = 109 . When the temperature is zero.6 Kittel & Kromer. Section 7. Chapter 7 8.Chapter 8 Bose-Einstein Condensation Key Concepts • Macroscopic occupation of the ground state • Critical Temperature • Superﬂuid 4 He • Trapped Atomic Gases • Simple Physical Picture Reading Schroeder. all of the N atoms will be in the ground state which has an energy of h2 3h2 12 + 12 + 12 = (8.

BOSE-EINSTEIN CONDENSATION By taking the Taylor expansion of the denominator.110 CHAPTER 8.8) (8.11) (8.6) Hence for low temperatures µ(T ) is very close to the energy of the ground state. so the ground state energy will be approximately zero and so the chemical potential will also be close to zero.7) −1 We can approximate this sum by N = ≡ N0 + ∞ 0 g(ε) 1 ε−µ kB T T ∂ε −1 (8.612 V vQ (8.13) .12) is 2.5) (8.12) The value of the integral in equation (8.612 2πmkB T h2 V = 2. since the energy of the ground state approaches zero as the volume becomes large and we have a large system at low temperature.4) kB T ε0 −µ (8. thus giving Ne (T ) = 2. we can ﬁnd that the chemical potential as a function of temperature is given by N0 = = Rearranging for µ gives kB T As T → 0 µ(T ) ∼ ε0 − = N0 1+ ε0 −µ kB T −1 1 (8. In three dimensions 2 g(ε) = √ π 2mπ h2 3 2 V √ ε (8. The chemical potential can also be determined by N= s nBE (εs ) = s 1 e εs −µ kB T T (8.9) e N0 (T ) + Ne (T ) Where g(ε) is the density of states and Ne (T ) is the number of atoms in an excited state.10) We assume that µ(T ) = 0.3) (8.315. We now get that Ne (T ) is given by Ne (T ) = = 2 √ pi 2 √ π 2πm h2 3/2 V 3 2 ∞ 0 √ ε∂ε ε 2πmkB T h2 e kB T T − 1 ∞ √ x∂x ε where x = x−1 e kB T 0 3 2 (8.

is equal to the total number of particles. We deﬁne the critical temperature Tc as the temperature at which the number of excited particles. as the temperature approaches the critical temperature. MACROSCOPIC OCCUPATION OF THE GROUND STATE 111 Where vQ is the quantum volume.14) So. which can be written as 2 kB Tc = 0. . that is they were in the ground state.15) The fraction of particles in the ground state of a system of bosons is given by 3 N0 (T ) 1 − T 2 T < Tc Tc = (8. approaches zero. for temperatures greater than the critical temperature the assumption that µ(T ) = 0 is no longer valid. V N. vQ . Ne (Tc ) = N (8.16) 0 N T > Tc Note thate Bose-Einstein condensation occurs approximately when the quantum volume. which is the cube of the de Broglie wavelength of a single particle. is equal to or greater then the volume per particle. Since the initial assumption that µ(T ) = 0 was based on the fact that the energy of most particles was zero. A Bose-Einstein condensate forms when the temperature is below the critical temperature. Ne . the number of particles in the ground state.8.527 2πm N V 2 3 (8. We can see from the equation for Ne that as T increases the value of Ne also increases.1. N0 (T ).

1: Photocopy – Number of atoms in ground state.2: Photocopy – Schematic representation of energy scales Figure 8.112 CHAPTER 8. and superﬂuid drawings . BOSE-EINSTEIN CONDENSATION Figure 8.3: Photocopy – Phase diagrams of Helium. and chemical potential graphs Figure 8.

3 Why Does Bose-Einstein Condensation Occur? Why does Bose-Einstein condensation not occur for distinguishable particles? If we have a system of N distinguishable particles. EXAMPLES OF BOSE-EINSTEIN CONDENSATION 113 8.2. the internal energy will be of the order of N times the thermal energy of a single particle. at temperatures below Tc = 2. For the system. we can consider the whole system of N distinguishable particles. 8. So the probability of the system being in an excited N N 1 then Z1 > e−N and so the state is of the order ∼ Z1 e−N .1 Examples of Bose-Einstein Condensation Liquid Helium-4 (4 He) Liquid Helium-4 undergoes a transition to a superﬂuid phase. so U ∼ N kB T so the Boltzmann factor reduces to roughly e−N . The observed critical temperature was Tc 10−7 K.2. which is very small. into a volume of the order of 10−15 m3 . and given particle has a certain probability of occupying a single particle state with an energy ε less than kB T . 8. on the order of Z1 . About 104 atoms were conﬁned. However the total number of system states is extremely N large. Below the critical temperature the liquid can be viewed as a mixture of normal liquid and superﬂuid components. −U A system state with energy U has a Boltzmann factor e kB T . Since the probability of a particle being in the ground state is then Z1 the ground state is very low.2. By 1999 Bose-Einstein condensates had been observed with dilute gases of atomic sodium.17K. which is going to be a very large number. lithium and hydrogen.2 Dilute Gases of Weakly Interacting Gases Bose-Einstein condensation was ﬁrst observed for dilute gases in 1995 by Wieman et all using Rubidium-87. it will be diﬃcult to form a Bose-Einstein Condensate. and if Z1 probability of the system being in an excited state is extremely close to 1.8. In 1962 Landau recieved a Nobel prize for his theory of superﬂuidity and in 1978 Kapitsa also recieved a Nobel prize for his work in superﬂuidity. Superﬂuidity in helium-4 was discovered by Kapitsa.2 8. Allen and Misener in 1938. This suggests that the superﬂuid component is a Bose-Einstein condensate It is necessary to consider the interactions between the helium atoms to explain the superﬂuidity. using laser cooling and trapping. Alternatively. with essentially zero viscosity. Then the probability of a particle being in 1 1. The number of possible states a particle could be in is Z1 . The Nobel prize in 2001 went to Wieman and Ketterle for their work in the ﬁeld of Bose-Einstein condensates. The Superﬂuid state involves macroscopic quantum coherence. . similar to that responsible for superconductivity.

and is given by eZ1 N Z1 N N + Z1 − 1 N Z1 ∼ Ns ∼ (8. thus allowing for a Bose-Einstein condesate to form. The number of system states is roughly the number of ways of arranging N units of energy among Z1 . if Z1 N .4 N Two Fluid Model of Superﬂuidity For Bose-Einstein condensates = The total number of bosons = N0 (T ) + Ne (T ) = Number of bosons in the ground state + Number of bosons in excited states The density.1 contains a comparison of some of the properties of the superﬂuid and normal ﬂuid components. which has inﬁnite thermal conductivity.18) Table 8.Ns . with an energy U ∼ N kB T is much smaller than for distinguishable particles. the heat is transferred throughout the ﬂuid immediately. Thus it is impossible to set up a temperature gradient within the ﬂuid. and the e−N term becomes more signiﬁcant making the probability of the system being in an excited state very low. then the probability of the system being in an N then eZ1 If Z1 N excited state is again very close to 1. This is because thermal conduction within the 4 He occurs via the superﬂuid component.114 CHAPTER 8. no bubbles Table 8.1: Properties of normal and super ﬂuids viscosity thermal conductivity entropy Superﬂuid 0 ∞ 0 Normal Fluid non-zero ﬁnite nonzero form when it is heated. N 8. then the total number of states is not very large. of the Bose-Einstein condensate is the sum of the density of the superﬂuid component and the density of the normal ﬂuid component. Heat transfer within a . ρ. Superﬂuid 4 He does not boil. BOSE-EINSTEIN CONDENSATION For a system of N identical bosons the number of systems states . and so if one part of the ﬂuid is heat.17) eN N Z1 N Z1 ≥ e−N . which is required to form bubbles. That is. and is given by ρ = ρs (T ) + ρn (T ) (8. However.

If a heat source is placed somewhere within a superﬂuid. and the superﬂuid component moves in the opposite direction. TWO FLUID MODEL OF SUPERFLUIDITY 115 superﬂuid occurs by the movement of the normal component. This motion occurs under the constraint that the total density remains constant throught the superﬂuid. .8. the normal ﬂuid component moves from the source towards the sink.4. and a heat sink placed elsewhere within the superﬂuid.

116 CHAPTER 8. BOSE-EINSTEIN CONDENSATION Figure 8.4: Photocopy – Speciﬁc heats of 3 He and 4 He .

For a superleak this is not possible because only the superﬂuid can pass from 1 to 2 and the superﬂuid carries no entropy. Suppose T1 were to slowly increase.4.19) = µ2 = ∂µ2 .4.1 Superleaks A Superleak is a ﬂow of the superﬂuid component through a highly porous material that the normal ﬂuid component cannot pass through due to viscosity. Thus the ﬂuid carries entropy from 1 to 2.5: A superleak If in the system shown above T1 > T2 and P1 = P2 then for a normal connection thermal equilibrium is reached by the conduction of heat.8. Figure 8. TWO FLUID MODEL OF SUPERFLUIDITY 117 8. For thermal and diﬀuse equilibrium to hold it is required that µ1 ∂µ1 Using the thermodynamic indentities G = µN = U − T S + P V and T ∂S = ∂U + P ∂V − µ∂N We get the equation N ∂µ = −S∂T + V ∂P From the conditions for equilibrium we know that ∂µ = 0 (8.

.4. which since V remains constant. The heater in the main section raises T1 above T2 . causes P1 to S become greater than P2 which forces the superﬂuid throught the capillary.2 Thermomechanical Eﬀect It is possible to establish a pressure diﬀerence between two superﬂuids connected by a superleak by creating a temperature diﬀerence.118 And so CHAPTER 8. BOSE-EINSTEIN CONDENSATION µ1 − µ2 = 0 = −S(T1 − T2 ) + V (P1 − P2 ) Therefore T1 − T2 V = S P1 − P2 This leads to several interesting phenomena (8. Figure 8.6: A fountian based on the thermomechanical eﬀect The capilary in the diagram contains a superleak.21) 8.20) (8.

3K ∆T 1mK ∼ ∆z cm That is a temperature diﬀerence of only 1mK will produce a height diﬀerence of 1cm. by creating a pressure diﬀerence between two systems connected by a superleak will cause a temperature diﬀerence to arise. This is in contrast to a normal ﬂuid. For superﬂuid 4 He at around T = 1. The magnitude of this eﬀect can be found as follows V ∆T = ∆P S let ∆P = ρg∆z This gives ρg ∆T = ∆z S (8.4.22) Where ρ is the mass per mole and S is the entropy per mole.8.3 Mechanocaloric Eﬀect Similarly. TWO FLUID MODEL OF SUPERFLUIDITY 119 8. for which a pressure diﬀerence causes a mass ﬂow.4. The quantitative details of this eﬀect have been experimentally veriﬁed. .

120 CHAPTER 8. BOSE-EINSTEIN CONDENSATION .

Scientiﬁc American.Chapter 9 Magnetic Phase Transitions Key Concepts • Curie Temperature • Order Parameter • Continous First Order Phase Transitions • Ising Model • Mean-Field Theory • Failure of Mean-Field Theory • Exact Solutions • Correlation Functions • Critical Exponents • Universality of Critical Exponents Reading Schroeder. Section 8.M.2 P. Wilson.G. Ising Program K. Solid State Simulations. Principles of Condensed Matter Physics Silsbee and Drager. 241. Lulenslay. Chailin and T.C. 158-179 (August 1979) 121 .

1: Phase diagram for a ferromagnet 9. M= 1 N < mi >= i i s mi (s) −ε(s) e kB T Z (9. (9.1) In the absence of an applied magnetic ﬁeld . MAGNETIC PHASE TRANSITIONS Tc Paramagnet T Figure 9. the magnetisation M has the property M = 0 for T > Tc M = 0 for T < Tc Where Tc is known as the Curie Temperature. B = 0.3) lMI ferromagnet T Tc B=0 paramagnet Figure 9.2) (9. Cobalt and Nickel all have a phase diagram of the general form Let M be the average magnetic moment per atom.1 Ferromagnet-Paramagnet Phase Transition Ferromagnets such as Iron.122 external B field CHAPTER 9.2: Absolute magnetisation vs temperature for a ferromagnet .

but one must take into consideration the interactions between magnetic moments to get an accurate description.4) (9.g. The answer is yes. melting ice.9.1. The phase transition is a continous phase transition. Cv (T ) = −T ∂2F → ∞ as T → Tc ∂T 2 ∂2F → ∞ as T → Tc χ(T ) = ∂B2 (9. There are singularities in the second-order derivatives of the Helmholtz free energy at T = Tc . when Ising gave an exact solution of the two dimensional Ising model. as opposed to a ﬁrst-order phase transition (e. This was only answered deﬁnitively in 1944. FERROMAGNET-PARAMAGNET PHASE TRANSITION 123 There is no latent heat associated with the phase transition. this makes the maths a lot more diﬃcult. Unfortunately. This is because the quantities M= ∂F ∂B T and S=− ∂F ∂T B are both continous at T = Tc . .5) A question that lies at the core of statistical mechanics is can statistical mechanics describe phase transitions such as these. etc) for which there are discontinuities in the ﬁrst-order derivatives of the Helmholtz free energy F .

3: Photocopy – Molar heat capacities of four ferromagnetic copper salts . MAGNETIC PHASE TRANSITIONS Figure 9.124 CHAPTER 9.

g. Consider an inﬁnite lattice of points C (e.g. a cubic lattice).4: Nearest neighbours for a square lattice for each i.2. THE ISING MODEL 125 9.7) In the hamiltonian the sum over < ij > represents that for each spin i the product si Sj is summed for each of the nearest neighbours of i. It is the simplest known model that can describe a continuous phase transition. Let z be the number of nearest neghbours for the lattice C. si sj is summed over the 4 nearest neighbours.2 The Ising Model The Ising model was introduced in 1925.9.6) si (9. Suppose T = 0 and B = 0 For J > 0 the ground state is a ferromagnet ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ ↑ 1 N ↑ ↑ ↑ o r ↓ ↓ ↓ ↓ ↓ ↓ ↓ ↓ ↓ ↓ ↓ ↓ M= i < si >= ±1 For J < 0 the ground state is an antiferromagnet ↑ ↓ ↑ ↓ ↑ ↓ ↑ ↓ ↑ ↓ ↑ ↓ ↑ ↓ ↑ . e. At each point i ∈ C there is a classical spin si = ±1 The Ising hamiltonian in a magnetic ﬁeld B is H = −J si sj + µB <ij> i∈C (9. for the square lattice Figure 9.

8) Where {si } denotes the sum over all possible 2N spin conﬁgurations for the N spins in the system.9) . MAGNETIC PHASE TRANSITIONS We want to evaluate the partition function of the Ising model at ﬁnite non-zero (T > 0) temperatures. In 1944 Onsager produced an exact solution to the two dimensional Ising model on a square lattice that gave the Curie temperature as Tc = J 2 √ kB T log 2 − 1 2.27 J kB T (9. In general. evaluating this sum is an impossible task except for one or two dimensional systems. Z= {si } e kB T ( 1 −J P <ij> si sj +µB P i si ) (9.126 CHAPTER 9. the Ising model describes a phase transition at a Curie temperature Tc greater than zero. For three dimensions it is necessary to make approximations. For more than one dimension.

1: Photocopy – Assorted tables on critical temperatures . THE ISING MODEL 127 Table 9.2.9.

The solution to this hamiltonian was found earlier in the course in the Paramagnetism section (Section 3). This simpliﬁes to si sj m0 (T ) (si + sj ) 2 (9. We can now evaluate the partition function as Z = zN µBef f kB T (9.17) where z = 2 sinh .16) (9. In the hamiltonian we now make the substition si s j → 1 (si < sj > +sj < si >) 2 (9. the same value will be found.12) Substituting this into the Ising hamiltonian simpliﬁes it into H = (µB − Jzm0 (T )) ≡ µBef f i si i (9.10) We take the average of the average spin as being equal to the average spin because we assume that the system is invariant under translation. For the Ising model let m0 (T ).14) si Where Bef f .128 CHAPTER 9.13) (9. so that if we calculate m0 (T ) from two diﬀerent places within the lattice.15) The simpliﬁed hamiltonian is the hamiltonian for a two-state paramagnet in an eﬀective ﬁeld. By judiciously replacing certain terms in the equations with the average values. MAGNETIC PHASE TRANSITIONS 9. known as the Mean-Field. the average spin be given by m0 (T ) ≡ 1 N si = si i (9.3 Mean-Field Theory The Mean-Field Theory can be used to simplify problems such as the Ising model by assuming that the conditions throughout the system do not greatly vary.11) Basicly the product of the spins is equal to half of the ﬁrst spin by the average of the second spin plus half the average of the ﬁrst spin by the second spin. the eﬀective magnetic ﬁeld is given by Bef f = B − Jzm0 (T ) µ (9. it is possible to greatly simplify the problem without losing important details.

we require that < si >= m0 (T ) (9.18) µBef f kB T (9.9. The mean-ﬁeld approximation of the Ising model thus gives the Curie temperature as being Tc = zJ kB T (9. the magnetisation of the stable ferromagnetic states approaches zero.26) Comparing the results obtained using mean-ﬁeld theory with experimental results and exact solutions.20) = − = tanh kB T −B For this result to be consistant with our initial approximation. B The second case is for t < 1 The equation in this case has three solutions. Then zJm0 (9. .19) (9. So m0 (T ) = 0 for T > kzJT .3. and one at each of y = ±y0 . the equation has only one solution. The ﬁrst case is for t ≥ 1 In this case. the value of m0 approaches 1.25) (9. Table 9. one at y = 0.23) (9. while the solutions at y = ±y0 correspond to stable ferromagnetic states.2 compares the values of kB Tc for one J an two dimensions given by exact and mean-ﬁeld methods.21) To ensure this we equate m0 (T ) with the equation found for < si >. MEAN-FIELD THEORY The average spin is then given by < si > = 1 Z si (a)e kB T e − e−x = − tanh(x) = −tanh ex + e−x m0 (T )Jz µ a x ε(a) 129 (9. The solution at y = 0 corresponds to an unstable antiferromagnet. we ﬁnd that mean-ﬁeld theory qualitatively describes the transition.24) There are two cases to consider for the solutions of m0 . and solve for m0 (T ). but it is quantitatively unreliable unless the number of nearest neighbours is large. and as t approaches zero. We consider the system with no applied magnetic ﬁeld.22) m0 = tanh kB T Introduce two new variables y and t deﬁned as kB T zJ zJm0 m0 = y= kB T t t= substituting these into the equation for m0 we get ty = tanh y (9. B = 0. Note that as t approaches 1. which is y = 0.

2 0 −0. MAGNETIC PHASE TRANSITIONS Solutions of m0 for t ≥ 1 1.8 −0.4 −0.4 0.6: ty and tanh y vs y for t < 1 .8 0.4 −0.6 −0.8 −1 −1 −0.5 −1 −0.6 tanh y 0.5 ty −1 −1.5 1 0.6 −0.4 −0.5 tanh y 0 −0.8 1 Figure 9.2 0 y ≡ m0/t 0.6 −0.6 0.2 0.2 ty (t > 1) −0.5: ty and tanh y vs y for t ≥ 1 Solutions of m0(T) for t < 1 1 0.6 0.8 −0.8 1 Figure 9.130 CHAPTER 9.4 0.2 0.2 0 y ≡ m0 / t 0.4 0.

27 4 Figure 9.2: Values of kB Tc from exact and mean-ﬁeld methods J Dimensions exact Mean-Field 1 0 2 2 2.3.8: Photocopy – Failure of mean-ﬁeld theory .7: Mean magnetisation vs temperature Table 9.9. MEAN-FIELD THEORY 131 l m o(T) Tc T Figure 9.

speed = 70 T =3 T =2 Note that as T decreases. and then tried to see if the spin will ﬂip. between each step. Suggested settings to try and compare the results of are T = 7. the lattice is updated and a new value of the magnetization is calculated. and the number of steps taken.27 the entire lattice aligns itself into one spin. 1000 steps. T = 2: B=0 B = +0. the speed at which the program displays the spin changes. Then the Ising model gives a reasonable description of the liquiﬁcation of a gas.132 CHAPTER 9. Both programs are based on the Ising model. the probability of each spin ﬂipping is calculated. and the magnetic ﬁeld corresponding to the pressure of the system. B = 0.5 B = −0. but the N´el program considers more e interactions between the spins. the size of regions of of similar spin increases.4 Solid State Simulations The Solid State Simulations package includes contains two programs which e deal with spin interactions. applied magnetic ﬁeld.. The hamiltonian of the system will be N =−1 H = −J one possible microstate is i si ↑ 1 +1 ↓ 2 -1 ↑ 3 +1 ↑ 4 +1 sn sn+1 N =1 sn = ±1 (9. size of the lattice. .. the power spectrum of the magnetization or the autocorrelation function of the magnetization. These programs are Ising and N´el. For example. The display on the right can show a plot of the magnetization as a function of time. the initial conditions. .5 The Ising model can also be used to describe other systems. When the program is run. 9. consider an up spin corresponding to the presence of an atom...5 Exact Solution Of The Ising Model In One Dimension Consider a chain of N spins in the absence of a magnetic ﬁeld. with an up spin represented by a red block and a down spin represented by a white block. The display on the left shows a lattice of spins..27) ↑ 5 +1 ↓ 6 -1 ↑ 7 +1 . a down spin corresponding to the lack of an atom. It is possible to vary the temperature. ↑ N +1 . until when T < Tc = 2.. The programs have two displays. MAGNETIC PHASE TRANSITIONS 9. Once this is down for each spin.

30) This result is independent of the value of sN as the sum over sN is the same for sN −1 = 1 and sN −1 = −1..31) This last term again reduces to 2 cosh J regardless of the value of sN −2 .33) 1. We can make this approximation when N Now that we have the partition function of the system we can calculate the internal energy of the system ∂ ln Z ∂T ∂ ln 2 cosh = N kB T 2 ∂T J U (T ) = −N J tanh kB T U = kB T 2 J kB T (9.5. .34) The high and low temperature limits of the internal energy are U (T ) = −N J 2 − N JT kB for low temperatures.35) Note that U (T ) is a smooth function of T . there are no phase transitions for non zero temperatures. EXACT SOLUTION OF THE ISING MODEL IN ONE DIMENSION133 The partition function can be written as Z= s1 =±1 s2 =±1 s3 =±1 ..32) = N (9. we do the sum over sN e−JsN −1 sN sN =±1 = e−JsN + eJsN = 2 cosh J (9. as T approaches zero J for large T where T kB T (9. Now the partition function becomes Z = 2 cosh J s1 =±1 s2 =±1 s3 =±1 . First. . ..28) Where J = . Because of this. Thus Tc = 0.29) (9. e−JsN −2 sN −1 (9. .. . sN −1 ±1 e−Js1 s2 e−Js2 s3 .9. sN ±1 J kB T e−Js1 s2 e−Js2 s3 . By continuing to reduce each sum to 2 cosh J we ﬁnally get Z = s1 =±1 2 cosh 2 2 cosh 2 cosh J kB T J kB T J kB T N −1 N −1 (9. e−JsN −1 sN (9. There are 2N terms in the sum.

G(n) = si si+n (9. which is the distance over which spins tend to be aligned with each other. In terms of the Correlation distance.3 contains the numerical values of these critical exponents calculated from mean-ﬁeld and exact methods. kB T ξ(T ) ∼ (9.41) (9. as the temperature approaches the Curie temperature. ξ. and the heat −α− . χ(T ) ∼ (T − Tc ) .42) and ξ(T ) ∼ 9.36) It is possible to rewrite the Correlation function in terms of what is known as the Correlation length. And as the temperature approaches the capacity. . CV (T ) ∼ (Tc − T ) Curie temperature from above in the absence of a magnetic ﬁeld the heat −α capacity has the form CV (T ) ∼ (T − Tc ) + .40) (9. a x number of the properties of the system follow the general form of |T − Tc | . is proportional to the probability that the spin at lattice site i is related to the spin at a distance n from it. the exponents are known as critical exponents. the correlation length becomes (9. MAGNETIC PHASE TRANSITIONS 9. Table 9. G(n).134 CHAPTER 9.6 Correlation Functions and Lengths The Correlation function. the correlation length as a function of temperature is ξ(T ) = −1 ln tanh In the low temperature limit.37) In one dimension. these include the magnetization. In general. M (T ) ∼ (Tc − T ) .39) 1 k2JT e B approaches ∞ as T approaches 0 2 So as the temperature is lowered. In the absence of a magnetic ﬁeld adn approaching the Curie temperature from β below. as does the magnetic −γ suceptability.38) J kB T J.7 Critical Exponents In the Ising model. For these properties. the the correlation between spins increases. for d dimensions G(r) = sx sx+r −|r| 1 e ξ(T ) d−2+η |r| 1 |T − Tc |ν (9. the Correlation function is G(n) = e −n ξ (9.

27 J 9. Also.9. when the number of dimensions is three or more. 9.8. For this he recieved the Nobel proze in 1982. UNIVERSALITY OF CRITICAL EXPONENTS 135 Table 9. Explaining the unversality of critical exponents and calculating their values was a major challenge to research in statistical mechanics.1.8 Universality of Critical Exponents In general the value of the critical exponents only depend on the number of dimensions of the system and the number of components n of the order parameter. . Example 9.3: Critical Exponents For the Ising model in two dimensions mean-ﬁeld exact α 0 0 1 1 β 2 8 7 γ 1 4 kB Tc 4 2.2. Mean-ﬁeld theory did get the phase diagram qualitatively correct which is a useful result. Example 9. They do not depend on the microscopic details of the hamiltonian. The Ising model (n = 1) with a square lattice has the same critical exponents as the Ising model with a rectangular lattice. A superﬂuid and a two dimensional ferromagnet both hvae n = 2 and the same critical exponents. a number of Nobel prizes have been awarded for work using mean-ﬁeld theory so it may be a good way to hedge your bets for the future. Theories describing a number of important and interesting phenomena such as the BCS theory of superconductivity and the dynamical mean-ﬁeld theory of strongly correlated metals are mean-ﬁeld theories. the accuracy of mean-ﬁeld theory increases.8.8. Fianlly.9 Mean-Field Theory Isn’t All Bad! Despite the fact that for the Ising model in two dimensions mean-ﬁeld theory gave numerical results that were larger than the exact solutions. it is not necessarily bad. A triumph of theoretical physics in the 1970’s was the introduction of the renormalisation group by Wilson.

MAGNETIC PHASE TRANSITIONS .136 CHAPTER 9.

2 C. “Where Drunkards Hang Out”.B. Ch. Physics with Illustrative Examples From Medicine And Biology. 2 F.M.html 137 . Vol 2: Statistical Physics. Random Walks and Diﬀusion Key Concepts • Random Walks • Frictional Forces • Langevin Equation • Einstein Relation • Determination of Avagadro’s Number • Fluctuation-Dissipation Theorem • Diﬀusion Equation • Fokker-Planck Equation Reading D. Handbook of Stochastic Methods Nature. Statistical Physics: an Introductory Coourse.phys. Benedek. 686-7 http: www.edu/classes/109N/more stuﬀ/Applets/brownian/brownian.W. Ch.virginia.Chapter 10 Brownian Motion. Gardiner. 413. Villars and G. Ina Stewart.H.J Amit & Verbin.

Suppose a particle starts at the origin and then takes a step of distance L in a random direction n (|n| = 1). BROWNIAN MOTION.1 A Brief History of Brownian Motion 1827. R.2 Random Walks In Brownian motion it was observed esperimentally that the average position. Langevin 1908. Einstein’s explanation of Brownian motion. 1905.5) = RN + L n = RN (10. Here D is known as the diﬀusion coeﬃcent. However the average distance of the particle from the origin increases with time. 1926. providing the 10. This process is repeated N times. R =0 Here denotes the average over many trajectories. The position of the particle at the (N + 1)th step compared to the N th step is RN +1 = RN + Ln with R0 = 0 Taking the average over many trajectories RN +1 since n = 0.RN 2 2 (10. Therefore RN = R0 = 0 (10.1) = 2dDt (10.3) The distance from the origin squared of the particle at the (N + 1)th step in terms of the distance from the origin at the N th step is |RN +1 | = |RN | + L2 + 2Ln. The botanist Robert Brown observes random motion of particles (pollen grains with radii ∼ 1µm) in water.6) . J.2) Where d is the number of dimensions of the system. Perrin uses Einstein’s theory to measure kB T = ﬁrst precise determination of Avagadro’s number. of the particle over many trajectories was zero.4) (10. |R| 2 (10. Einstein’s theory was very important because it was ﬁrmly established the existance of atoms. RANDOM WALKS AND DIFFUSION 10. Perrin recieves Nobel prize in physics Historically. We can see that this is so by looking at some simple considerations.138CHAPTER 10. R NA . 1908.

2. RANDOM WALKS 139 Figure 10.10.1: A random walk .

by iteration we ﬁnd that |RN | = N L2 (10. BROWNIAN MOTION. After z some time the particle will reach it’s terminal velocity.3 Frictional Forces Consider a particle of mass M moving in a viscous medium.140CHAPTER 10. that is n is independent of RN . The equation of motion of the particle is M ∂r ∂2r = Fc (t) +µ ∂t2 ∂t (10.3. we can replace n. For water η ∼ 10−2 Poise and 1Poise = 1P = 0. However.1 Terminal Velocity Suppose the mass is falling due to the force of gravity. so the entire term goes to zero. which is given by vt = mg µ (10. the average over many trajectories is taken.12) 10.13) where Fc (t) is the force on the particle due to collisions. n = 0.4 The Langevin Equation Consider a “large” particle of mass M in a gas or liquid at temperature T . Fg = −mgˆ. Thus we get |RN +1 | 2 = |RN | 2 + L2 (10.RN (10.9) 10. The molecules in the ﬂuid will collide with the particle at random times. 10. RN . RANDOM WALKS AND DIFFUSION Once again.10) where µ is the coeﬃcent of friction.1kgm−1 s−1 .7) Because n and RN are unrelated.11) where η is the viscosity coeﬃcent of the medium. Stokes showed that if the mass is a sphere of radius a then the coeﬃcent of friction is given by µ = 6πaη (10. Fc (t) will be a random function of time. Thus the diﬀerential equation is a stochastic .RN with n . |RN +1 | 2 = |RN | 2 + L2 + 2L n. It experiences a force due to friction F = −µv = −µ ∂r ∂t (10.8) Since the particle starts at the origin.

Because of this we can multiply the equation by r to get r. ∂2r ∂r + µr.Fc (10.15 we get M ∂2 2 µ ∂ 2 r = dkB T r + 2 ∂t2 2 ∂t We solve this diﬀerential equation of r2 with the initial condition r2 (t = 0) = 0 and ∂ 2 r (t = 0) = 0 ∂t (10. 2 ∂t ∂t (10.r) = 2r.14) To continue we note that the following relations occur ∂r ∂ ∂r2 = (r. and so by the equipartition theorem equal to two times the number of dimensions by 1 kB T .18) The solution to the diﬀerential equation is r(t)2 = −µt 2dkB T M t+ e M −1 µ µ (10.19) . 2 M ∂r ∂t 2 1 = 2d kB T = dkB T 2 (10.4. By using these relationships on the stochastic diﬀerential equation we can rewrite it as M ∂2 2 µ ∂ 2 r + r −M 2 ∂t2 2 ∂t ∂r ∂t 2 = r.Fc (t) = M r.r) = 2r.Fc = r .10.16) And since there is no special direction in the gas Fc = 0.17) By substituting these into the average of Eqn 10. we can simplify the average of the M ∂r term. 2 Also. THE LANGEVIN EQUATION 141 diﬀerential equation. r and Fc are unrelated so r. 2 + 2 ∂t2 ∂t ∂t ∂t where r = |r|. The average is twice ∂t the average kinetic energy.15) We now take the average of this equation over the “ensemble” of all possible trajectories (Forces) of the ﬂuid particles which are collinding with the large particle. Fc (10. ∂t ∂t ∂t and 2 ∂ 2 r2 ∂2 ∂2r ∂r = 2 (r.

22) This is the Einstein relation..20) t M So for short amounts of time. Equating the consant with the diﬀusion coeﬃcent D we get D= kB T µ (10. the particle moves with a constant speed. t µ . leaving r(t)2 = 2dkB T µ t (10. 10. − 1 −µt 1 + M 2 µt M = = sdkB T µ M µt 1 + µ M 2 dkB T 2 (10. For a particle with a radius of about 1µm and a mass of about 5 × 10−12 kg. the exponential term dies away. where R is the ideal gas constant and NA is Avagadro’s number. the ratio of M to µ will be of the order of ten to the seventh seconds. we expand the exponential using a taylor series to M µ M µ 1 µt + M 2 µt M 2 2dkB T µ 2dkB T µ t+ t+ t− 1− µt M 2 2 + . BROWNIAN MOTION. . Then R using the Einstein relation and the fact that kB T = NA . RANDOM WALKS AND DIFFUSION For short times t get r(t)2 = M µ ..5 Perrin’s Determination of Avagadro’s Number from Brownian Motion The friction coeﬃcent µ of a ﬂuid can be determined from measuring the terminal velocity of particles moving through it. The diﬀusion coeﬃcent D can be measured by observing the Brownian motion of particles in the ﬂuid.23) µD The Eistein relation is one of the simplest examples of the ﬂuctuatuion-dissipation theorem which connects ﬂuctuations (in this case D describing Brownian motion) and dissipation (in this case the frictional coeﬃecent µ). we ﬁnd that Avagadro’s number is can be calculated as RT NA = (10.142CHAPTER 10. For M long time periods. Note that D is independent of the mass of the particle and that µ will depend on the size of the particle.21) This form of motion is brownian motion.

We then have N= ∞ −∞ dxf (x.33) .27) At a later time t + τ the density is given by f (x.25.24 the ﬁrst term on the right reduces to f . The integral in the second term on the right calculates the average value of ∆.28 we get f +τ ∂f =f ∂t ∞ −∞ d∆φ(∆) − ∂f ∂x ∞ −∞ ∆φ(∆)d∆ + ∂2f ∂x2 ∞ −∞ d∆ ∆2 (10.. t) − ∆ ∂x 2 ∂x2 f (x. and from Eqn 10. Suppose that in a time interval τ that a single particle experiences a shift in position between ∆ and ∆ + d∆ with probability φ(∆)d∆. so the average of ∆ is 0.30) Limiting these equations to only a few terms and substituting into Eqn 10. These are ∂f + ..6 Diﬀusion Equation and Brownian Motion For simplicity we consider one dimension. t) (10. ∂t ∂f ∆2 ∂ 2 f + + . t + τ ) = ∞ −∞ d∆φ(∆)f (x − ∆.24) (10. The probability distribution must satisfy the following conditions ∞ −∞ d∆φ(∆) = 1 (10. We can now reduce the equation to the diﬀusion equation ∂2f ∂f =D 2 ∂t ∂x where D≡ 1 τ ∞ −∞ (10.25) (10.28) We now take the Taylor expansion of f (x. t) with repect to ∆. t + τ ) with respect to τ and f (x − ∆.29) (10.6. Assume each particle is independent of all other particles. DIFFUSION EQUATION AND BROWNIAN MOTION 143 10.26) φ(∆) = φ(−∆) φ(∆) → 0 as |∆| → ∞ Suppose that the density of the particles f (x. the probability distribution of ∆ is even. f (x − ∆. t) = f (x.10. t + τ ) = f (x.31) φ(∆) 2 From Eqn 10. t) (10.32) ∆2 φ(∆)d∆ 2 (10. t) + τ (10... Consider N particles suspended in a volume V . t) at time t is non-uniform.

t. . in one dimension let P (p. t0 ) be the probability density for a particle with initial momentum p0 at time t0 to have a momentum p at time t. RANDOM WALKS AND DIFFUSION In general (three dimensions) ∂f = D 2f ∂t ∂2 ∂2 ∂2 = + 2+ 2 2 ∂x ∂y ∂z (10. This is the reason we had to have F (t)F (t ) = 2µkB T δ(t − t ) −p2 (10.36) is equivalent to the diﬀusion equation.34) 2 Conservation of particles means that a concentration gradient with a particle current jd = −D f Fick’s law ∂f + ∂t jd = 0 f is associated (10.7 Fokker-Planck Equation The Fokker-Planck equation describes the time development of the probability distribution function for the momentum (or velocity) of a diﬀusing particle described by a Langevin equation. ∂p = −γp + F (t) ∂t µ where γ = M (10.35) (10. For simplicity. 10.40) (10. p0 .144CHAPTER 10.41) was to ensure that the equilibrium solution would be correct. BROWNIAN MOTION.39) Here denotes an average over all possible conﬁgurations of the random force.38) (10. Then P satisﬁes the Fokker-Planck equation ∂ ∂ 1 P ∂P = µkB T + P ∂t ∂p kB T m ∂p The time independent solution to this diﬀerential equation is P = Peq (p) = conste 2mkB T Which is the Gibbs factor.37) Here F (t) is a random time-dependent force which has correlations of the form F (t) F (t)F (t ) = 0 = 2µkB T δ(t − t ) (10.

Chapter 11 Transport Theory and the Boltzmann Equation Key Concepts • Transport Coeﬃcents • Non-equilibrium Distribution Function • Boltzmann Equation • Relaxation Time Approximation • Derivation of the Diﬀusion Constant • Drude Model Reading Ashcroft & Mermin. Ch 13 11.1 Transport Coeﬃcents From experiments we know • Ficks Law jd = −D n describes the diﬀusion of particles in a ﬂuid 145 (11. Solid state Physics.1) .

146CHAPTER 11. TRANSPORT THEORY AND THE BOLTZMANN EQUATION • Ohm’ Law je = −σ φ (11.2) where σ is the conductivity and φ is the electric potential describes the ﬂow of electrons in the material. • Fourier’s Law jh = −K T describes the spread of heat throughout a material with thermal conductivity K. D,σ, and K are examples of Transport Coeﬃcents. They are intensive quantities and have a unique value for any given material at a particular temperature and pressure (thermodynamic state). The purpose of transport theory is to derive these (linear response) coeﬃcents from statistical mechanics. (11.3)

11.2

Distribution Function

Consider a classical gas of N moecules. Due to the presence of external forces the gas is not quite at thermal equilibrium. For example, due to the presence of an electric ﬁeld there is a net ﬂow if charged molecules. let f (r, v, t) is the distribution function of the system and f (r, v, t)∂ 3 r∂ 3 v is the number of molecules inside a volume ∂ 3 r around r that have a velocity v to within ∂ 3 v. n(r, t) = is the local density. ∂ 3 vf (r, v, t) (11.4)

11.3

Free Particle Evolution (Liouvile’s Theorem)

Suppose the molecules do not collide with one another. The dynamics of the system is then ∂r =v (11.5) ∂t ∂v 1 = F (11.6) ∂t m where F is the external force. Thus in a small time ∆t all the particles with a velocity V at r at time t are located at r = r + v∆t = O(∆t)2 and have a velocity F v = v + ∆t + O(∆t)2 m (11.7) (11.8)

11.4. THE BOLTZMANN EQUATION Conservation of probability (or number of particles) requires that f (r, v, t)∂ 3 r∂ 3 v = f (r , v , t + ∆t)∂ 3 r ∂ 3 v

147

(11.9)

From phase space theory it can be shown that ∂ 3 r∂ 3 v = ∂ 3 r ∂ 3 v , and so f (r, v, t) = f (r + v∆t, v + F ∆t, t + ∆t) m (11.10)

**By taking a Taylor expansion of this and ignoring second order and higher terms in ∆t we ﬁnd dv dr ∂f + . rf + . ∂t dt dt ∂f 1 + v. r f + F. ∂t m
**

vf vf

=0 =0

(11.11) (11.12)

11.4

The Boltzmann Equation

Suppose the particles in the gas can undergo collisions. This will cause f (r, v, t) to change with time • It will increase because particles with diﬀerent velocities v will be scattered so they now have a velocity v. • It will decrease because particles with a velocity v will be scattered into a diﬀerent velocity v . In general ∂f + v. ∂t

rf

+

1 F. m =

vf

∂f ∂t collisions in out ∂f ∂f − ∂t coll ∂t coll =

(11.13) (11.14)

11.5

**Relaxation Time Approximation
**

− (f − f0 ) ∂f = ∂t coll τ

Assume that (11.15)

Where τ is the relaxation time. The relaxation time is just a “number” which we introduce into the theory, i.e. we don’t calculate it from “ﬁrst principles”. f0 is the equilibrium distribution function for the same density as f e.g. f0 (r, v) = const × e 2kB T

−M v2

148CHAPTER 11. TRANSPORT THEORY AND THE BOLTZMANN EQUATION

11.6

Uniform Solution

Suppose the system has a non-equilibrium distribution of velocities fi (v) at time t equal to zero and no external ﬁeld is present then −1 ∂f = (f − f0 ) ∂t τ which has the solution f (v, t) = f0 (v) + (fi (v) − f0 (v)) e

−t τ

(11.16)

(11.17)

Hence the system decays exponentially fast (within time τ ) into the equilibrium state.

11.7

Diﬀusion Constant From the Boltzmann Equation

Consider an isothermal system with a density gradient in the x direction. No external ﬁelds are present. In the steady state, the Boltzmann equation becomes vx −1 df = (f − f0 ) dx τ (11.18)

**let f = fo + δf where f0 is the local equilibrium distribution and equals f0 = const × e kB T T
**

µ(x)−ε

(11.19)

Here we are assuming that the density n(x) varies slowly with x so that we are able to deﬁne a local chemical potential. Working to the ﬁrst order in δf we have f = f0 − vx τ df0 dx f0 dµ df0 = dx kB T dx (11.20) (11.21)

**The particle ﬂux density is Jx =
**

∞ −∞

vx f (ε)N (ε)dε

(11.22)

**where N (ε) is the density of states. Substituting Eqns 11.20 and 11.21 into the ﬂux density equation gives
**

x J x = J0 −

dµ kB T dx τ

∞ −∞

2 vx f0 (ε)N (ε)dε

(11.23)

OHMS LAW AND THE DRUDE MODEL FOR FERMIONS x Where J0 . In general.24) since if there is no gradient the nubmer of particles going in the positive x direction must be equal to the number going in the negative x direction. D= kB T τ m (11.27) = = ∞ −∞ d (11.35 we ﬁnd that the diﬀusion constant is given by J x = −τ D= or τ 2 (11.31) 11. the particle ﬂux in the absence of a gradient. is given by x J0 = ∞ −∞ 149 vx f0 (ε)N (ε)dε = 0 (11.33) f0 (ε.26) (11.25 we get kB T dn (11.32) |v| 3 Note that the disﬀusion constant is determined by the equilibrium value of a particular ﬂuctuation.29) f0 (ε)N (ε)dε = number of particles at x = n(x) dn(x) dx dµ 1 dx kB T = Combining these into Eqn 11.8.30) m dx Substituting this into Eqn 10. so E = − dφ x.8 Ohms Law and the Drude Model For Fermions Consider an electron gas in the presence of an electric ﬁeld E = φ.25) If we note that the following relationships exist 1 m 2 v = kB T 2 x 2 ∞ −∞ (11. Thus the total particle ﬂux is Jx = −τ dµ 2 v kB T dx x ∞ −∞ f0 (ε)N (ε)dε (11. Let the electric ﬁeld be purely in the x direction.28) N (ε) dx f0 (ε)dε ∞ f (ε)N (ε)dε −∞ 0 dµ 1 dx kB T n(x) (11. linear response transport coeﬃcents are determined by ﬂuctuations in the equilibrium state.11. x) = ε−µ0 +eφ(x) e kB T +1 . The local equilibrium dx ˆ distribution function is 1 (11.

150CHAPTER 11.35) for temperatures signiﬁcantly less than the fermi temperature.34) (11. TRANSPORT THEORY AND THE BOLTZMANN EQUATION By an analysis similar to that used for the diﬀusion constant one ﬁnds an electric current density jx = −e2 The conductivity is then σ = e2 τ 2 N (εf )vf 3 dφ τ dx ∞ −∞ dεN (ε) − df0 dµ 2 vx (11. .

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