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Thermodynamics and Statistical mechanics exam to finding the solutions to canonical partition function problems in Physics.

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Damian Dailisan

1

Harmonic Oscillator

1.1

Continuous

**For the classical treatment of continuous energies, the Hamiltonian of 1 harmonic oscillator in 1 dimension is
**

1

p2

+ mω 2 q 2

2m 2

We solve for the corresponding Canonical partition function in one dimension

H=

Zi =

Zi =

Zi =

Zi =

Z

1

e−βHi dpdq

h

Z

Z

p2

1

1

2 2

−β 2m

dp e−β 2 mω q dq

e

h

1/2

1/2

1 2mπ

2π

h

β

βmω 2

2π

hβω

(1)

(2)

(3)

(4)

(5)

**where (4) is obtained by using a gaussian integral. However, since we have N atoms that
**

are distinguishable, the total partition function is

Z=

ZiN

=

2π

hβω

N

.

(6)

Now that we have Z, we can calculate the energy by

F = −kT ln Z

∂(βF )

U=

∂β

∂ ln Z

U =−

∂β

N

U=

β

(7)

(8)

(9)

(10)

**and hence, the energy of N classical harmonic oscillators is simply
**

U = N kB T .

(11)

**Knowing the relationship of the heat capacity and energy, we obtain the CV as follows:
**

1

2. .2 (13) Discrete For a harmonic oscillator with discrete energies. 1 − e−β¯hω (19) n n X e−β¯hωn = n where the subtitution of the summation is valid since x 1 so now. . then Z= ZiN = 1 csch(β¯hω/2) 2 2 N . 1. The we can express the summation as X e−β¯hωn = X xn . (24) . we may express Z as e−β¯hω/2 . we may simplify the above result by using cschx = ex 2 . 2 For one such harmonic oscillator. − e−x hence. the discretized energies are given by 1 n = h ¯ ω(n + ). Zi = β¯hω/2 e − e−β¯hω/2 Zi = (20) (21) By the definition of the hyperbolic cosecant function. n = 0. the partition function is given by X Zi = e−βn (14) (15) n Zi = e−β¯hω/2 X e−β¯hωn (16) n Let us make a substitution of x = e−β¯hω . (22) 1 Zi = csch(β¯hω/2) 2 (23) Since we have N distinguishable oscillators. . 1 − e−β¯hω 1 .CV = ∂U ∂T (12) CV = N k B 1. as in the quantum treatment. (17) n n X x = (1 − x)−1 . (18) 1 .

namely high temperature when T h ¯ ω. and low temperature when T h ¯ ω. Using the binomial expansion at the denominator (1 + x)n = 1 + nx for x 1. (29) Using the above. the energy is −¯hωcsch(β¯ hω/2) coth(β¯ hω/2) N 4 csch(β¯hω/2) 2 U = −1 U= (25) Nh ¯ω h ¯ω coth 2 2kB T (26) Now. we get the expression U= ¯ω ¯ω Nh ¯ω − h − h 1 + e kB T 1 − e kB T . T h ¯ ω. We can express the energy differently as − h ¯ω Nh ¯ ω 1 + e kB T U= . We may expand the exponential about 0 since the exponent will be small. T h ¯ ω. (30) At high temperatures. First we re-express U in terms of exponentials: h ¯ω − h ¯ω Nh ¯ ω e 2kB T + e 2kB T U= . let us examine two extreme conditions for U . 2 1 − e− kh¯BωT (31) − h ¯ω It follows from T h ¯ ω that the exponent is large. 2 (32) (33) Following from (12). we can now get the heat capacity for the system of hamonic oscillators with discretized energies as. The expansion is as follows: ex = ∞ X xn n n! . (27) 2 e 2kh¯BωT − e− 2kh¯BωT At high temperatures. CV = Nh ¯ω h ¯ω −¯hω (−csch2 ) 2 2kB T 2kB T 2 N CV = 4kB h ¯ω T 3 2 csch2 h ¯ω 2kB T (34) (35) . 2 Nh ¯ω − 2¯hω U= 1 − e kB T .From (9). (28) x e ≈ 1 + x. we will get the energy for high temperatures to be U ≈ N kB T . hence the term e kB T is small.

the Hamiltonian of their magnetic interaction is given by H = −µH N X where σj = ±1. (37) Ω(E. Following H for on such atom. ND = 2 µH (39) (40) (41) (42) so now the microcanonical partition function is Ω(E. N ). N ) = 1 2 N! E N − µH ! 12 N + E µH (43) ! From the microcanonical partition function. 2 µH E 1 N+ . N ) = (38) where NU is the number of atoms with spin up and ND is the number of atoms with spin down. σj (36) j There are two posible states. we can obtain the Entropy as hown in the equation S = kB ln Ω(E. 1 E NU = N− . The total energy is given by E = −µH(NU − ND ). E = −µH(2NU − N ).2 Ising Model For N atoms with spin 1/2. then the number of states is as follows: N! . (47) j Zi = eβµH + e−βµH . (48) Zi = 2 cosh(βµH). 1 E 1 E S = kB ln N ! − ln N− ! − ln N+ ! . 2 µH 2 µH (44) (45) We can use Stirling’s approximation ln N ! ≈ N ln N − N and get N E N E N E N E − ln − − + ln + . If we have N such atoms. S = kB N ln N − 2 2µH 2 2µH 2 2µH 2 2µH (46) We can obtain the canonical partition of the system of N atoms by first considering one atom only. NU !ND ! N = NU + ND . we have Zi = X e−βµHσj . (49) 4 . that is spin up or spin down.

∂β 1 N N Z − − U =− . we can now have an integral of the following form: Z ∞ −xn 2 dx = n Z ∞ u1/n−1 e−u du. one where the potential is dependent on q n rather than q 2 as in our harmonic oscillator. Since we have N atoms. (60) . The integral now becomes 1 Zi = h 2mπ β 1/2 2π βmω 2 1/n Z ∞ n e−x dx. 0 Z ∞ −∞ 1 u1/n−1 e−u du = Γ . we can calculate the energy by once again the following ∂ ln Z . n assumes even integer values.3 Generic Potentials Let us consider a potential of a more generic term. For a system of N atoms in one dimension. (53) −∞ and if we make another substitution u = xn . the energy we obtain is simply U= N N + 2 n 5 kB T . In this case. n (57) Now that we have Z. the Hamiltonian is given by 1 p2 + mω 2 q n H= 2m 2 We solve for the corresponding Canonical partition function as follows: Z 1 Zi = e−βHi dpdq h Z ∞ Z p2 1 1 2 n −β 2m e−β 2 mω q dq. du = nu1−1/k dx. Zi = dp e h −∞ (50) (51) (52) We will now make a simple substitution xn = β 12 mω 2 q n such that dx = β 12 mω 2 dq. e dx = Γ n n −∞ e (54) (55) (56) where we used the definition of the gamma function to evaluate the integral in (55). the total partition function will then be Z= ZiN 1 = N h 2mπ β N/2 2π βmω 2 N/n 2 Γ n N 1 . n 0 Z ∞ 1 2 −xn . Z 2 n β U =− (58) (59) and hence.

This integral is fairly trivial to solve by integrating by parts. (68) h Z ∞ V Zi = 3 e−βpc 4πp2 dp. we have pc mc2 such that we have E ≈ pc. Z 2π Z π Zi = dφ eβµH cos θi sin θdθ. (69) h 0 where we have shifted to spherical coordinates to simplify the integration. We can solve for the partition function of the system by integrating over phase space for one particle: Z 1 Zi = 3 e−βE d3 pd3 q. each with energy given by p E = p2 c2 + m2 c4 . (66) (67) In the ultrarelativistic limit.4 Paramagnetism: Vector Spins In Section 2 we discussed paramagnetism using the Ising model approach. where p2 = p2x + p2y + p2z . Here. Zi = 0 (62) (63) 0 2π (64) eβµH − e−βµH . the partition function is thus Zi = ZN 1 Z= i = N! N! 6 8πV β 3 c3 h3 N . we get the partition function Zi = 1 ZN Z= i = N! N! 5 4π sinh (βµH) βµH N . (65) Ultrarelativistic Gas Consider N particles in 3 dimensions. βµH (eβµH −e−βµH ) Substituting sinh βµH = and considering our system has N such indistin2 guishable atoms. Hi = −~µ · H (61) From the Hamiltonian we may already obtain the partition function and get Z e−βHi dΩ. from which we will get 8πV . (70) β 3 c3 h3 Taking into account that we have N particles and indistinguishability. The Hamiltonian for one atom is given by ~ = −µH cos θi . we will try to solve the more general form for vector spins. (71) .

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