Statistical Thermodynamics

Microscopic World: molecules

Energy levels
Molecular properties

Macroscopic World: bulk

Internal energy
Pressure
Entropy
Temperature
Statistical Thermodynamics

Microscopic World

H ψ n = Enψ n

Macroscopic World

F = −kBT ln Z
 Statistical Thermodynamics
Ludwig Eduard Boltzmann (1844-1906)

The father of the kinetic theory of gases and of statistical mechanics,

he was a Stephan’s student and supervised (among others) Arrhenius and Nernst
For his work, he had strong opponents such as Mach
 Why statistical?
It is in principle possible to predict the
detailed behavior of few dice provided
appropriate information on their
“initial” state is available

With many dice we face the problem of the lack of

appropriate information on the “initial” state..

..but we can easily predict the average

behavior of tons of dice, provided we
assume equal likelihood for each face to
show up
 Why statistical?

It is in principle possible to predict the detailed

behavior of few molecules provided appropriate
information on their “initial” state is available

With many molecules we face the problem of the lack of appropriate information
on the “initial” state..

We can easily predict the average behavior

of N>>> 1 molecules provided we assume
equal likelihood for states with equal
energy
 Why statistical?

Some numbers..
18 g di H20 (18 ml) = NA molecules, i.e.
we need to know
9NA = 9 x 6.022 x 1023 initial position and momenta
(in classical mechanics)
(ca. 5 Y variables, “Y=yotta=1024”)

ca. 1014 Tb to store them in dp!

[ ca. 102 Yb ]
Statistical Thermodynamics I: the concepts

Basic assumption
Principle of equal a priori probability

(for our purposes)

In thermodynamic equilibrium
states with equal energy have equal probability
Statistical Thermodynamics I

Proof I Proof II
“physical” “mathematical”

Boltzmann distribution
&
Partition function
 Statistical Thermodynamics I

Boltzmann distribution
&
Partition function

Averages of mechanical
Entropy
observables

Temperature
Statistical Thermodynamics I

Proof I Proof II
“physical” “mathematical”

Boltzmann distribution
&
Partition function
 Proof I

• the system S needs to be (quasi) isolated, i.e. large

enough to make “interactions” negligible (large
Volume/Surface ratio): 𝐸 ≈ 𝐸# +𝐸% (for each level)

• S small enough to be tractable

 Proof I
i i' f f'
State* I: E , E
S R
State* F: E , E
S R

i i' f f'
E +E =E +E
S R S R

I F
Principle of equal probability P =P
i i' f f'
Statistical independence PP =P P
S R S R

*I ≡ (i, i'), F ≡ ( f , f ')

 Proof I
f i'
P S P R
=i f'
P S P R
The ratio can only depend on system properties..
ΔES = E Sf − ESi, ES = (E Sf + ESi ) / 2
The ratio cannot depend on absolute energies..
ΔES = E Sf − ESi, ES = (E Sf + ESi ) / 2
 Proof I

ε2
ε1

f (0) = 1
..from the principle of equal probability
 Proof I

f is a universal function of the energy difference Δε

f (0) = 1
f (Δε31 ) = f (Δε32 ) f (Δε 21 )
....
 Proof I

g = ln f is a universal function of the energy difference Δε

g(0) = 0
g(Δε31 ) = g(Δε32 ) + g(Δε 21 )
g(nΔε ) = ng(Δε )
g(Δε / n) = g(Δε ) / n
hold for arbitrary Δε
 Proof I

g = ln f is a universal function of the energy difference x

g(0) = 0
g(x + y) = g(y) + g(x)
g(α x) = α g(x)
g is a linear function of the energy difference!!
 Proof I
g(Δε ) = ln f (Δε ) = −βΔε
εi
ε0

Fix ε 0
as a reference and let εi
vary
 Proof I

εi

Z = C = ∑e
−1 − βεk ..normalization “constant”
k
Z = Z(β, N, X1,..X n )
Proof I

For each state i

εi

Z = ∑e − βεk

partition function
Zustandssumme
 Proof I

no upper bound
εi

lower bound

Z = ∑e − βεk
<∞ only for β >0
k 1
..we shall see later β=
k BT
Remark 1
 Proof I

εi

− β ( x1+x2 ) − β x1 − β x2
e =e e
Extensivity Statistical
independence

Remark 2
Statistical Thermodynamics I

Proof I Proof II
“physical” “mathematical”

Boltzmann distribution
&
Partition function
 Proof II

….

ε1 ε 2 ε3 ε 4 ε 5 ε 6 ....
n1 n2 n3 n4 n5 n6 ....
N = ∑ nk
“Configuration” k

[n1, n2 , n3, n4 , n5, n6 ,...]

[25, 0, 0, 0, 0, 0,...] W =1
N = 25 [23, 2, 0, 0, 0, 0,...] W = 25x24 / 2 = 300 “Weight”
[20, 3, 2, 0, 0, 0,...] W = 531300
 Proof II
N!
W[n1,n2 ,n3,..] =
n1 !n2 !n3 !..

….
ε1 ε2 ε3 ....
n1 n2 n3 ....
S1S2 S3..Sn1 | Sn1+1Sn1+2 ...Sn1+n2 | Sn1+n2 +1..Sn1+n2 +n3 |..
N! rows

S2 S1S3..Sn1 | Sn1+1Sn1+2 ...Sn1+n2 | Sn1+n2 +1..Sn1+n2 +n3 |..

S3S2 S1..Sn1 | Sn1+1Sn1+2 ...Sn1+n2 | Sn1+n2 +1..Sn1+n2 +n3 |..
S1S3S2 ..Sn1 | Sn1+1Sn1+2 ...Sn1+n2 | Sn1+n2 +1..Sn1+n2 +n3 |..
n1! n2! n3!
 Proof II
N!
W[n1,n2 ,n3,..] =
n1 !n2 !n3 !..
“Multinomial coefficient”

sum over n1, n2,..nk

under constraint
 Proof II

lnW = ln N!− ∑ ln nk ! ~ N ln N − ∑ nk ln nk
k k

ln N! ~ N ln N − N Stirling’s approximation

Let’s seek the maximum of lnW

under constraints

N = ∑ nk Fixed number of realizations

k
Fixed total energy of the ensemble..
E = ∑ nkε k ..or equivalently fixed average system energy
k
 Proof II

lnW = ln N!− ∑ ln nk ! ~ N ln N − ∑ nk ln nk
k k

ln N! ~ N ln N − N Stirling’s approximation

Let’s seek the maximum of lnW

under constraints

N = ∑ nk Fixed number of realizations

k
Fixed total energy of the ensemble..
E = ∑ nkε k ..or equivalently fixed average system energy
k
 Proof II
constraints

𝛿 𝑁ln𝑁 − + 𝑛, ln 𝑛, + 𝛼𝛿 𝑁 − + 𝑛, + 𝛽𝛿 𝐸 − + 𝑛, 𝜖, = 0
, , ,

Lagrange’s multipliers

+ 𝛿𝑛, ln 𝑛, + 1 + 𝛼 + 𝛽𝜖, = 0
,

−1−α − βεk − βεk

nk = e e = Be
i.e. the Boltzmann result for pk = nk / N
 Stirling’s approximation
ln N! ~ N ln N − N
∞ ∞
Γ(n) = ∫ x n e− x dx =[−x n e− x ]∞0 + n ∫ x n−1e− x dx =nΓ(n −1) Γ(0) = 1
0 0

Γ(n) = n!
n −x n ln x−x f (x)
g(x) = x e = e =e
1
f (x) = f (n) + f ''(n)(x − n)2 ..
2

∞ 1 n
n ln n−n −a( x−n)2
n ln n−n+ ln(2 π n) #n&
Γ(n) ~ e ∫e dx ~ e 2
= 2π n % (
$e'
0
Further information 1
 Lagrange’s multipliers
without constraints..
∂f ∂f
∂f ∂f = =0
df = dx1 + dx2 = 0 ∂x1 ∂x2
∂x1 ∂x2
grad g grad f
with constraint g(x1, x2 ) = 0 ? dx
" ∂f ∂f % " ∂g ∂g %
df = $ , ' ( dx1, dx2 ) = 0 dg = $ , ' ( dx1, dx2 ) = 0
# ∂x1 ∂x2 & # ∂x1 ∂x2 &
!
dx is not arbitrary, has to be orthogonal to ∇g
! ∇f ∇g, i.e. ∇f + α∇g = 0
∇f ⊥ dx
Further information 2
 Lagrange’s multipliers

Equivalently, look at the stationary points of

L(x1, x2 ) = f (x1, x2 ) + α g(x1, x2 )

without constraints
!
dL = ( ∇f + α∇g) dx = 0
i.e.
∇f + α∇g = 0

and choose that solution x = x(α ) which satisfies g(x) = 0

Further information 2
 Statistical Thermodynamics I

Boltzmann distribution
&
Partition function

Averages of mechanical
Entropy
observables

Temperature
 Mechanical observables

For each state n

En
e − β En
p(En ) =
Z
Z= ∑e − β En

H ψ n = Enψ n
for any observable A ∑ n
A e − β En

A = ∑ pn An = n
An = ψ n  ψ n n ∑e − β En

n
(ψ n ψ n = 1)
 Mechanical observables

For each state n

En
e − β En
p(En ) =
Z
Z= ∑e − β En

H ψ n = Enψ n
e.g. the energy E ∑ n
E e − β En

E = ∑ pn En = n
En = ψ n H ψ n n ∑e − β En

n
(ψ n ψ n = 1)
 Mechanical observables

For each state n

En
e − β En
p(En ) =
Z
Z= ∑e − β En

∂
∑E en
− β En
− ∑e
∂β n
− β En

∂
E = ∑ pn En = n
= = − ln Z
n Z Z ∂β

Remark 1
 Mechanical observables

− β ( En −E0 ) − β E 'n
Z = ∑e − β En
=e − β E0
∑e =e − β E0
∑e =e − β E0
Z0
n n n
Z0 is referenced to the
− β En − β E0 − β ( En −E0 ) − β E 'n ground-state
e e e e
pn = = − β E0
= − β E 'k
∑e − β Ek
e Z0 ∑e
k k

∂ ∂ ∂
E = − ln Z = − (−β E0 + ln Z 0 ) = E0 − ln Z 0 = E0 + E '
∂β ∂β ∂β

The zero of energy is irrelevant for

Remark 2 statistics but affects the average E value
 Mechanical observables
Z0 has a simple meaning..

Z0 = ∑ e − β (En −E0 )
= 1+ e − βΔE1
+e − βΔE2
+.. ≥ 1
n
excitation energies ΔEk ≥ 0

e− βΔEn
pn =
Z0
β →∞ β →0

Remark 2 β →∞ β →0
 Mechanical observables
Independent systems

𝐸4 H = HA + HB
𝐸4 = 𝐸56 + 𝐸57
𝐼 = (𝑖; , 𝑖= )

𝑍 = + 𝑒 AB(CD6 ECD7 ) = + + 𝑒 ABCD6 𝑒 ABCD7 =

56 ,57 56 57
ABCD6
= +𝑒 + 𝑒 ABCD7 = 𝑍; 𝑍=
56 57
 Mechanical observables
Independent systems

𝐸4 H = HA + HB

𝐸4 = 𝐸56 + 𝐸57
𝐼 = (𝑖; , 𝑖= )

𝑒 AB(CD6 ECD7 ) 𝑒 ABCD6 𝑒 ABCD7 𝑒 ABCD6

𝑝5;6 = + 𝑃5657 =+ = + ≡
𝑍 𝑍; 𝑍= 𝑍;
57 57 57
 Mechanical observables
Independent (and distinguishable)
molecules
𝐸4
H = hA + hB + hC +..
𝐸4 = 𝜖56 + 𝜖57 + 𝜖5I +. .

N
Z = z A zB zC ... identical molecules Z=z
z = ∑e − βεk
molecular partition function
k
{εk } molecular energy levels (states)
 Mechanical observables
Particle in a box (1D)

p2 !2 d 2
h= +V = − 2
+V (x)
2m 2m dx

$ 0 −L / 2 ≤ x ≤ L / 2
V =%
& ∞ | x |> L / 2

2 2 ∞
nh z = ∑e − βε n 2 ∞ − βε n 2
εn =
8mL2
= n 2
ε n = 1, 2,.. ≈ ∫ 0
e dn =
n=1

1 +∞ − x 2 π 2π m L
β not too large
2 βε
∫ −∞
e dx =
4 βε
=L
βh 2
=
λβ
 Mechanical observables
Particle in a box (3D)

h = hx + hy + hz

'
h 2 ! n 2x n y n 2z $
2 )) nx = 1, 2,..
εn = ## 2 + 2 + 2 && ( ny = 1, 2,..
8m " Lx Ly Lz % )
)* nz = 1, 2,..

L x L y Lz V β
z = z x z y zz = 3
= 3 λβ = h
λβ λβ 2π m
1
..we shall see that β =
k BT
 Mechanical observables
Particle in a box (3D)

h = hx + hy + hz

'
h 2 ! n 2x n y n 2z $
2 )) nx = 1, 2,..
εn = ## 2 + 2 + 2 && ( ny = 1, 2,..
8m " Lx Ly Lz % )
)* nz = 1, 2,..

Example: H2 in 100 cm3 @298.15 K

h 6.626 ×10 −34 Js

λβ = = = 7.12 ×10 −11 m
2π mkBT 2π × 3.347 ×10 −27 kg ×1.38 ×10 −23 JK −1 × 298.15K
10 −4 m 3 26
z= = 2.77 ×10 for D2 lb is 2 smaller
(7.12 ×10 −11 m)3
 Mechanical observables
Particles in a box (3D)
N
!V $
Z = z N = ## 3 &&
" λβ %

ln Z = N ( lnV − 3ln λβ )

∂ ∂ #% 3 h 2 &( 3N d ln β 3N
E = − ln Z = − N % lnV − ln β − 3ln ( ≡ =
∂β ∂β $ 2 2π m ' 2 d β 2β

β 3 1
λβ = h U(T ) −U(0) = NkBT = E β=
2π m 2 k BT
 Mechanical observables
Particle in a harmonic well (1D)

p2 !2 d 2
h= +V = − 2
+V (x)
2m 2m dx

1
V = mω 2 x 2
2

∞ ∞
! 1$ − β !ω n − β !ω n 1
ε n = !ω # n + & n = 0,1, 2,.. z0 = ∑ e = ∑(e ) =
" 2% n=0 n=0 1− e− β !ω
β !ω n
Note.. Sn = ∑ x k Sn x = x n+1 + Sn −1
−
z=e 2
z0
k=0
 Mechanical observables
Particle in a harmonic well (1D)

1
z0 =
1− e− β !ω

e− β !ω n
pn = = e− β !ω n (1− e− β !ω )
z0
Example: molecule I2

hc ν
ν = 214.6 cm −1
hcν = !ω β !ω = ν=
k BT νT
@T = 298.15K pn = 0.645e−1.036n
ν T = kBT / hc = 207.226 cm −1 p0 = 0.645, p1 = 0.229, p2 = 0.081
 Mechanical observables
Particle in a harmonic well (1D)

1
z0 =
1− e− β !ω

e− β !ω n
pn = = e− β !ω n (1− e− β !ω )
z0

∞
1 ∞ − β !ω n 1 1 dz0 1 d ln z0
n = ∑ n pn = ∑ ne =− =− =
n=0 z0 n=0 z 0 !ω d β !ω d β
1 kT
− β !ω β →0 ≈ = B
1 d − β !ω e 1 β !ω !ω
= ln (1− e ) = − β !ω
= β !ω
!ω d β 1− e e −1 β →∞ ≈ e− β !ω
 Mechanical observables
Particle in a harmonic well (1D)

1
z0 =
1− e− β !ω

e− β !ω n
pn = = e− β !ω n (1− e− β !ω )
z0

1 1
β →0 ≈ !ω + ≈ kBT
1 1 !ω 2 β
ε = !ω + !ω n = !ω + β !ω
2 2 e −1 1
β →∞ ≈ !ω
2
 Mechanical observables
N Particles in a harmonic well (3D)
e.g. Einstein model
1
z0 =
1− e− β !ω

3N β !ω 3N β !ω
− −
− β !ω −3N
Z =e 2
Z0 = e 2
(1− e )

3N
β →0 ≈ ≈ 3NkBT
3N 3N 3N!ω β
E= !ω + 3N!ω n = !ω + β !ω
2 2 e −1 3N
β →∞ ≈ !ω
2
 Mechanical observables
Rigid rotor
p⊥2 J2 J2 J = re r̂ ∧ p ≡ re r̂ ∧ p⊥
h= = 2
=
2m 2mre 2I p ⊥2 = J 2 / re2

B = ! 2 / 2I

J 2ψ m, j = ! 2 j( j +1)ψ m, j j = 0,1, 2..

m = − j, − j +1,.. j −1, j
Em, j = Bj( j +1)
The sum is over
(m,l) states, not ∞ j ∞
z = ∑ ∑ e− β Bj ( j+1) ≡ ∑ (2 j +1)e− β Bj ( j+1)
energy levels! j=0 m=− j j=0

∞
1 ∞ d '(e− β Bx( x+1) )* 1
β not too large ≈ ∫ e− β Bx( x+1) (2x +1)dx = − ∫ dx =
0 βB 0 dx βB
Mechanical observables
N Rigid rotors

N
N
" 1 %
Z =z ≈$ '
# βB &

ln Z ≈ −N ln ( β B)

∂ N
T not too small E = − ln Z ≈ = NkBT
∂β β
 Mechanical observables
N non-interacting spins-1/2

h = −mH 0 = µ B gsz H 0
1 1
γ = µB g s=− ,
2 2
βγ H 0 βγ H 0
− " βγ H 0 %
z=e 2
+e 2
= 2 cosh $ '
# 2 &
β γ H0 β γ H0
Low T (large b) z=e 2
(
1+ e
−β γ H0
)=e 2
z0
z0 →1
High T (small b)
z0 → 2
ln z = ln ( 2 cosh ( βγ H 0 / 2 ))
 Mechanical observables
N non-interacting spins-1/2

h = −mH 0 = µ B gsz H 0
1 1
γ = µB g s=− ,
2 2

βγ H 0
±
e 2
p± =
Low T (large b) ! βγ H 0 $
2 cosh # &
p0 →1, p1 → 0 " 2 %

High T (small b)
1
p0 , p1 →
2
 Mechanical observables
N non-interacting spins-1/2

h = −mH 0 = µ B gsz H 0
1 1
γ = µB g s=− ,
2 2
βγ H 0 βγ H 0
− " βγ H 0 %
z=e 2
+e 2
= 2 cosh $ ' Z = zN ln Z = N ln ( 2 cosh ( βγ H 0 / 2 ))
# 2 &

∂ γ H 0 sinh ( βγ H 0 / 2 ) γ H0
E = − ln Z = −N = −N tanh ( β γ H 0 / 2 )
∂β 2 cosh ( βγ H 0 / 2 ) 2

Low T (large b) High T (small b)

2
γ H0 #γ H0 &
E ≈ −N E ≈ −N β % (
2 $ 2 '
 Mechanical observables
N non-interacting spins-J

h = −mH 0 = µ B gsz H 0
γ = µ B g sz = −J, −J +1,.., J
J
sinh !"( J +1 / 2 ) x #$
zJ = ∑e kx x
, zJ e = zJ + e ( J+1) x
−e − Jx
zJ =
sinh ( x / 2 )
x = βγ H 0
k=− J

Low T (large b) High T (small b)

J(J +1) 2
E ≈ −NJ γ H 0 E ≈ −N β (γ H 0 )
3
 Fluctuations

pn ∝ e − β En Are average values representative enough?

E≤En ≤E+ΔE
p(E) = ∑ pn ∝ g(E)e− β E E ≈ Emax
n

..rapidly increasing ..rapidly decreasing

in general, for any extensive variable X

N
X = x1 + x2 +.. = ∑ xk X = Nx
k=1
N
2
X − X ≡ ∑ (xk − x) ( X − X ) ∑ k
= (x − x)(x n − x) ≡ ∑ k
(x − x) 2
= NΔx 2

k=1 k,n k

Remark 1 ΔX = N Δx
 Classical statistical mechanics
Translations and rotations
most often are classic

q ,p are the classical states

H(q,p) is the classical energy

ΔqΔp 1
z = ∑e − β H (qi , pi )
= ∑ e − β H (qi , pi )
≈ ∫ dq dpe − β H (q, p)

i ΔqΔp i h0

h0 is some fundamental constant with dimension energy x time

Remark 2
 Classical statistical mechanics
Translations in 1D

p2
h= +V
2m

$ 0 −L / 2 ≤ x ≤ L / 2
V =%
& ∞ | x |> L / 2

β p2 +∞ β p2
1 − L − L 2m +∞ − y2 L 2mπ
z=
h0
∫ dq dpe 2m
= ∫ dpe
h0 −∞
2m
=
h0
∫
β −∞
dye =
h0 β
h0 is the fundamental constant!
h0 = 2π !
Remark 2
 Classical statistical mechanics
Classical limit for N particles

q ,p are the classical states

H(q,p) is the classical energy

3N 3N
dq dp − β H (q1,q2 ,.. p1, p2 ..)
Z= ∫ h 3N
e

Remark 2
 Indistinguishability
Independent indistinguishable
molecules
En
H = h1 + h2 + h3 +..
single particle
h ⇒ {ε1, ε 2 , ε3,..ε k ,..} energies
Every (allowed)
configurations [n1, n2 , n3,..nk ,..] configuration is
one state
En = n1ε1 + n2ε 2 +.. + nkε k +.. = ∑ nkε k
k
nk = number of molecules in molecular state k
N = ∑ nk = total number of molecules
n
Remark 3
 Indistinguishability
Indistinguishable vs. Distinguishable
molecules
En
sum restricted to N-particle states

[N]
− β ( n1ε1+n2ε2 +..nkεk )
Z= ∑ e
n1,n2 ..nk

nk = 0,1 nk = 0,1, 2,..

Fermions (Fermi-Dirac statistics) Bosons (Bose-Einstein statistics)

Remark 3 Advanced topic, we need some trick..(different partition functions)

 Indistinguishability
Indistinguishable vs. Distinguishable
molecules
En
What is wrong in
Z=z ?N

At high enough T nk << 1 and we set nk ! = 1 Z dis ≈ N!Z

N
(Boltzmann statistics)
z
i.e. Z≈
Remark 3 N!
 Indistinguishability
Indistinguishable vs. Distinguishable molecules
Energies of
one-particle states T=0 K T>>0 K
Example: H2
e7 in 100 cm3 @298.15 K
e6
e5 λβ = 71.2 pm
e4 z = 2.77 ×10 26
e3
e2 pk ≤ p0 = z −1
e1
e0 ⇒ nk = Npk << 1
n0 = N nk = 1 k ≤ N, holds up to

nk = 0 k > 0 nk = 0 k > N N ≈ z = V / vβ or equivalently

p ≈ 1.14 ×10 5 p∅
Remark 3
 Indistinguishability
Indistinguishable vs. Distinguishable molecules
Volume available to each
In general.. molecule in the container
“Thermal volume”

3
N N 3 λ
n0 = Np0 = = λ β ≡ β << 1 ⇒ v >> λ 3β 1/3
" k BT %
∅ 1/3
z V v l ∅ = (v ) =$ ∅ '
10
3
#p &
2
10

1 e
length / Å

10 e in K
e in Na
e in Li
0
10
H2
h
10
-1 λβ =
N2 2π mkBT
-2

Remark 3
10 0 1 2 3 4
10 10 10 10 10
T/K
 Mechanical observables

For each state n

En
e − β En
p(En ) =
Z
Z= ∑e − β En

H = H (X)
X= “field” parameters ∑n
Y e − β En

En = En (X) Y = ∑ pnYn = n

n ∑e − β En

Y is called “generalized force” (conjugate to X)

 Mechanical observables

For each state n

En
e − β En
p(En ) =
Z
Z= ∑e − β En

..for any reversible change dX affecting the system H

d E = ∑ pn dEn + ∑ En dpn
n n

− “adiabatic” work ∝ entropy change

Remark
 Mechanical observables

d E = ∑ pn dEn + ∑ En dpn
n n

− “adiabatic” work ∝ entropy change

Remark
 Mechanical observables
X=V, Y=P
Particles in a box (3D)

h = hx + hy + hz
Shape is irrelevant in the
thermodynamic limit !
h2 ## nx = 1, 2,..
εn =
8mV 2/3
( x y z)
n 2
+ n 2
+ n 2
" ny = 1, 2,..
#
#$ nz = 1, 2,..

pressure

∂ε n 2 ε n 2 E NkBT
Pn = − =
∂V 3 V
P=
3V
=
V
PV = NkBT
Mechanical observables
X=H0, Y=M
N non-interacting spins-1/2

h = −mH 0 = µ B gsz H 0
1 1
γ = µB g s=− ,
2 2
∂ε n ε
mn = − ≡− n
∂H 0 H0

E γ
M ≡− = N tanh ( β γ H 0 / 2 )
H0 2

Low T (large b) High T (small b)

γ γ 2H0
M≈N M ≈ Nβ
2 4
Mechanical observables
X=H0, Y=M
N non-interacting spins-J

h = −mH 0 = µ B gsz H 0
γ = µ B g sz = −J, −J +1,.., J
∂ε n ε
mn = − ≡− n
∂H 0 H0

Low T (large b) High T (small b)

J(J +1) 2
M ≈ NJ γ M≈N βγ H 0
3
 Statistical Thermodynamics I

Boltzmann distribution
&
Partition function

Averages of mechanical
Entropy
observables

Temperature
 Entropy

For each state n

En
e − β En
p(En ) =
Z
Z= ∑e − β En

Entropy is an extensive measure of the “spread of the

system” over system states

S↔Z
 Entropy

For each state n

En
e − β En
p(En ) =
Z
Z= ∑e − β En

S = −kB ln p = −kB ∑ pn ln pn
n
..is extensive SAB = −kB ln pA pB = −kB ln pA − kB ln pB
..is monotonously growing
with the spread S → ∞ for pn → 0
 Entropy
“S is at a maximum for the distribution
describing the thermal equilibrium state”
More precisely, consider the arbitrary distribution
{π 1, π 2 , π 3,..., π n ,...}. Then,
Θ(π 1, π 2 ,..) = −kB ln π = −kB ∑ π n ln π n
n
is maximum when π n = pn = e− β En / Z
under the usual constraints

∑π n =1 ∑E πn n =E
n n
Justification
 Entropy

# & # & # &

d % −kB ∑ π n ln π n ( − α d % ∑ π n ( − β d % ∑ En π n ( = 0
$ n ' $ n ' $ n '

∑ dπ n
!"kB ( ln π n +1) + α + β En #$ = 0
n

hence, if { pn } is the Boltzmann distribution

S = Θ( p1, p2 ,... pn ) = Θmax

Justification
 Entropy
Equivalently, we
could have defined
ens
Θ = NΘ ≡ kB lnW
N

and
ens
S = NS ≡ kB lnWmax
N

Proof:
lnW ≈ N ln N − ∑ nk ln nk = N ln N − N ∑ π k ln ( N π k ) ≡ −N ∑ π k ln (π k )
k k k

Justification
 Entropy

ψ Hψ
Θ(π 1, π 2 ,..) = −kB ln π Ξ[ψ ] = H ψ
=
ψψ
at maximum for the at minimum for the
Boltzmann distribution ground state

S = Θmax E0 = Ξmin
..entropy.. ..ground-state energy..

Remark
 Entropy
N Particles in a box (3D)
e− β (n1ε1+..nkεk ..)
pn =
Z
N
z N
1 V ! $ h2β
Z= = ## 3 && λβ =
N! N! " λ β % 2π m

ln Z ≈ N ln z − N ln N + N

S = −kβ ln p = −kB −β E − ln Z = kB β E + kB N ( ln z − ln N +1)

Sackur–Tetrode ! Ve 5/2 $
3 S = kB N ln ## &
βE = N 3 &
2 " N λβ %
 Entropy
N Particles in a box (3D)

zN
Z= Z = zN
N!

! Ve 5/2 $ ! Ve3/2 $
S = kB N ln ## &
3 &
S = kB N ln ## 3 &&
" Nλβ % " λβ %

N " V / 2e3/2 %
Distinguishable Si = 2 × kB ln $$ 3
'' = S f − kB N ln 2 ΔS = kB N ln 2 > 0
2 # λβ &

N " V / 2e 5/2 %
Indistinguishable Si = 2 × kB ln $
$ ' ≡ Sf
3 '
ΔS = 0
2 # N / 2 λβ &
 Entropy
N Particles in a box (3D)
z NA
z NB
ZA = ZB =
NA! NB !

! V e 5/2 $ ! V e 5/2 $
SA = kB N A ln ## A 3 && SB = kB N B ln ## B 3 &&
" N Aλ β % " NBλ β %

V
V iA = V iB =
2 ΔS = kB (N A + N B )ln 2 > 0
V Af = V Bf = V

83
83Kr: 11.5% (A) 84Kr: 57.0% (B) λβ ≈ 84 λβ
 Entropy
N Particles in a box (3D)

! Ve 5/2 $
S = kB N ln ## &
3 &
" Nλβ %

" V ∅e 5/2 % " RTe 5/2 %

∅
S = nR ln $$ m 3 '' = nR ln $$ ∅ '
3 '
# N Aλ β & # p N Aλ β &

Example: Sm∅ of Ar @298.15 K mAr = 39.95amu λβ = 16 pm

∅
$ 4.12 ×10 −21 J × e 5/2 ' −1 −1
S = R ln & 5
m −2 −11 3)
= 18.6R = 155JK mol
%10 Nm × (1.60 ×10 m) (

[email protected] K: Sm∅ = 17.6 R, [email protected] K: Sm∅ = 14.2 R

 Entropy
N non-interacting spins-1/2

h = −mH 0 = µ B gsz H 0
1 1
γ = µB g s=− ,
2 2
γ H0
ln Z = N ln ( 2 cosh ( βγ H 0 / 2 )) E = −N tanh ( β γ H 0 / 2 )
2
γ H0 " γ H0 % ( " γ H 0 %+
S = kB β E + kB ln Z = −N tanh $ ' + NkB ln *2 cosh $ '-
2T # 2kBT & ) # 2kBT &,

Low T (large b) High T (small b)

S≈0 S ≈ NkB ln 2
 Entropy

S≈0
Low T (large b)

N non-interacting spins-1/2
S ≈ NkB ln 2

h = −mH 0 = µ B gsz H 0 High T (small b)

1 1
γ = µB g s=− ,
2 2
 Statistical Thermodynamics I

Boltzmann distribution
&
Partition function

Averages of mechanical
Entropy
observables

Temperature
 Temperature

d E X = ∑ En dpn = TdSX
En n

S = −kB ∑ pn ln pn
n

TdSX = −kBT ∑ dpn ( ln pn +1) =

n

= −kBT ∑ dpn (−β En − ln Z +1) ≡ β kBT ∑ En dpn β k BT = 1

n n

Note: ∑ dpn = 0
n
 Temperature

d E X = ∑ En dpn = TdSX
En n

when the Hamiltonian parameters X

are fixed pn can only change because of
a change in T

# e − β En e − β En &
dpn X
= % −En + 2 ∑ Ek e ( d β
− β Ek

$ Z Z k '
2

( )
dE X = −E 2 + E 2 d β = −ΔE 2 d β =
ΔE
k BT 2
dT > 0 CV > 0
 Reaching very low temperatures
S(H 0 ,T,V ) ≤ S(0,T,V ) dE = TdS − MdH 0

isothermal change of entropy

) # ∂S & ,
dE T = +−M + T % ( . dH 0
+* $ ∂H 0 'T .-

dE S = −MdH 0 adiabatic demagnetization

$ ∂S ' max
ΔECA ≈T& ) H0 < 0
% ∂H 0 (T
 Thermodynamic potentials

e − β En
pn = Z = ∑ e − β En
En Z n

S = −kB ln p

1
S = −kB ln p = −kB −β E − ln Z = E + kB ln Z
T

−kBT ln Z = E − TS F = −kBT ln Z
or equivalently.. e − β F = ∑ e − β En
n
 Thermodynamic potentials
-dynamics
H = H (N,V,..X)
thermo-
Canonical Ensemble T N,V,..X

Z = ∑e − β En

F = F(N,V,T, X..) = −kBT ln Z(N,V,T,..X)

 Thermodynamic potentials
N,V,..X H = H N,V ,.. X
H ψ n = Enψ n
Canonical Ensemble T

Z = ∑ e− β En F = −kBT ln Z
n

# ∂ln Z & 2 # ∂ln Z &

U = −% ( = k BT % (
$ ∂β 'V ,N,X $ ∂T 'V ,N,X

U−F
S=
State equation p=p(V,T,N..X) T
!
# ∂U & # ∂F &
p = −% ( = −% (
$ ∂V 'S,N,X $ ∂V 'T ,N,X
 Thermodynamic potentials

Single component
system, N
molecules
F(N,V,T)

-dwrev (other than pV)

dU = +TdS − pdV + µ dN +..YdX

dH = +TdS +Vdp + µ dN +..YdX A single thermodynamic
potential (as a function of its
dF = −SdT − pdV + µ dN +..YdX natural variables) contains
all necessary information
dG = −SdT +Vdp + µ dN +..YdX
 Thermodynamic potentials

extensive extensive
intensive intensive

For example.. Note:

" ∂U % " ∂H % " ∂U % " ∂H % " ∂F % " ∂G %
T = +$ ' = +$ ' µ =$ ' = $ ' = $ ' = $ '
# ∂S &V ,N,.. X # ∂S & p,N,.. X # ∂N &S,V ,.. X # ∂N &S, p,. X # ∂N &T ,V ,. X # ∂N &T , p,. X
" ∂F % " ∂G %
S = −$ ' = −$ ' G(α N, p,T ) = αG(N, p,T )
# ∂T &V ,N,.. X # ∂T & p,N,.. X
G(N, p,T ) = N µ (p,T )
 Thermodynamic potentials
Example: let’s compute µ(p,T) for a monoatomic gas..

N
z 1 !V $
N
h2β Number density Thermal volume
Z= = ## 3 && λβ = v λ 3
N! N! " λ β % 2π m n = N / V β = β

# eV &
F = −kBT ln Z ≈ −NkBT ln %% ( = NkBT ln ( nvβ ) − NkBT
3 (
$ Nλβ '
p,T are the natural variables
" pvβ %
G = F + pV ≈ NkBT ln ( nvβ ) = NkBT ln $ '
# k BT &
3/2
! pvβ $ ! p$ k BT " 2 π m % 5/2
µ = kBT ln # & = kBT ln # & ξβ ≡ =$ 2 ' ( k BT )
" k BT % " ξT % vβ # h &
 Thermodynamic potentials
Example: let’s compute µ(p,T) for a monoatomic gas..

Number density n = N /V Thermal volume vβ = λ 3β

Average number of molecules in state i

Fermi-Dirac occupation function Bose-Einstein occupation function

Remark
Single component isolated
T, p and µ
..Entropy is at a maximum
system with constant volume..

∂S 1 1
" ∂S % 1 = − =0
$ ' = ∂E A TA TB
# ∂E &V ,N,.. X T

∂S p p
= A − B =0
" ∂S % p ∂VA TA TB
$ ' =
# ∂V &E,N,.. X T

∂S µ µ
" ∂S % µ =− A + B =0
$ ' =− ∂N A TA TB
# ∂N &E,V .. X T
 T, p and µ
Single component system:
two intensive variables are enough!
T, p vs. T, µ
p is good only in the absence of external fields
single-particle energy in the gravitational field
Field-free free-energy per particle

mgz
−
k BT
p = p0 e
 T, p and µ

T is not really uniform..

Photodissociation and
photoionization
of N2 and O2
mgz
−
k BT
p = p0 e
Warm air from absorption
of solar radiation by ozone
 Statistical Thermodynamics II: applications
N,V,..X,T Z = ∑ e− β En F = −kBT ln Z
n

State equation p=p(V,T,N..X) dF = −SdT − pdV + µ dN +.. +YdX

Canonical Ensemble
# ∂F & # ∂F & " ∂F %
S = −% ( p = −% ( µ = +$ '
$ ∂T 'V ,N,X $ ∂V 'T ,N,X # ∂N &T ,V ,X

# ∂F & * ∂ # F &-
U = F + TS = F − T % ( ≡ −T 2 , % (/
$ ∂T 'V ,N,X + ∂T $ T '.V ,N,X
# ∂F & 2
* ∂ # F &-
G = F + pV = F −V % ( ≡ −V , % (/
$ ∂V 'T ,N,X + ∂V $ V '.T ,N,X

!
" ∂U % " ∂2 F % −1 # ∂p & # ∂2 F &
CV = $ ' ≡ −T $ 2 ' κ = −V % ( =V% 2 (
# ∂T &V ,N,X # ∂T &V ,N,X $ ∂V 'T ,N,X $ ∂T 'V ,N,X
 Ideal gases
N N
z " ez % independent,
Z≈ ≈$ ' indistinguishable molecules
N! # N &

z is the molecular partition function

h ≈ hK + hrot + hvib + hel

P2 J A2 J B2 JC2 ⎛ p 2k mk Ω2k q 2k ⎞
3N−6

hK = hrot = + + hvib = ∑ ⎜ + ⎟
2M 2I A 2I B 2I C k=1 ⎝ 2mk 2 ⎠

M = molecular mass J = angular momentum q,p = normal mode coordinates

P = c.m. momentum I = inertia tensor and momenta
W = normal mode frequencies
*confined motion in volume V

very similar to a particle in similar to a rigid rotor very similar to a harmonic

a 3D box oscillator
 Ideal gases
N N
z " ez % independent,
Z≈ ≈$ ' indistinguishable molecules
N! # N &

z is the molecular partition function

h ≈ hK + hrot + hvib + hel

z ≈ zK zrot zvib zel Few-state

problem
particle in a 3D Rigid-rotor
box (with caveats) Harmonic oscillator

thermodynamic potentials, heat capacity, etc..

 Ideal gases

z ≈ zK zint
exactly the same as for
a monoatomic ideal gas
function of T only
# ez &
F = −kBT ln Z ≈ −NkBT ln % ( = FK − NkBT ln zint
$N'
" ∂F %
µ = $ ' = µ K − kBT ln zint = µ K + µ int
# ∂N &T ,V

G = N µ = GK + N µ int
µ int = −kBT ln zint
 Ideal gases

z ≈ zK zint
exactly the same as for
a monoatomic ideal gas
SK is the Sucker-Tetrode
expression
# ∂F & # ∂FK & NkBT
p = −% ( ≡ −% ( =
$ ∂V 'T ,N $ ∂V 'T ,N V K K 5
C = C + NkB = NkB
p V
# ∂F & 2
S = − % ( = SK − N µ 'int
$ ∂T 'V ,N
E = F + TS ≡ EK + N µ int − NT µ 'int CV = C VK − NT µ ''int
H = G + TS ≡ H K + N µ int − NT µ 'int C p = C Kp − NT µ ''int
 Ideal gases

z ≈ zK zint

µ K ⇒ µ K + µ int
FK ⇒ FK + N µ int
GK ⇒ GK + N µ int
..any deviation from the monoatomic
ideal gas is contained in the “internal SK ⇒ SK − N µ 'int
chemical potential”! EK ⇒ EK + N µ int − NT µ 'int
H K ⇒ H K + N µ int − NT µ 'int
µ int (T ) = −kBT ln zint C V ⇒ C VK − NT µ ''int
C p ⇒ C Kp − NT µ ''int
 Ideal gases: rotational contribution
Linear molecules, Nrot=2

J 2 J A2 J B2
h= = +
2I 2I 2I
General: distances from
N the center of mass
I = ∑ mα dα2 (≡ µ r )
2

Diatomics: reduced mass

α =1
and relative distance

Low T zrot = 1+ 3× e−2θ /T + 5 × e−6θ /T + 7 × e−12θ /T + 9 × e−20θ /T ..

! 2 J(J +1) J = 0,1,..
E=
2I M = −J,.., J
E ∞ J2
High T dφ dJ −
4π −
4π T
!2 zrot ≈ ∫ e k BT
= × 2π ∫ dJJe 2 IkBT
= × 2 π k B T × I ≡
θ= h 2
h 2
0 h2 θ
2IkB
 Ideal gases: rotational contribution
Linear molecules, Nrot=2

J 2 J A2 J B2
h= = +
2I 2I 2I
General: distances from
N the center of mass
I = ∑ mα dα2 (≡ µ r )
2

Diatomics: reduced mass

α =1
and relative distance

Some numbers..
!
(1.05 ×10 −34 Js)2
µ = 1 amu, d = 1 A ⇒ θ 0 = −27 −20 2 −23 −1
= 24.1K
2 ×1.66 ×10 kg ×10 m ×1.38 ×10 JK

!2 H 2 :θ ≈ θ0
= 87.9K D 2: θ ≈ θ0 CO2: θ ≈ θ0
θ= 0.5 × 0.74 2
1.0 × 0.74 2
= 44.0K
2 ×16.0 ×1.16 2
= 0.56K
2IkB
 Ideal gases: rotational contribution
Linear molecules, Nrot=2

µ K ⇒ µ K − kBT ln(T / θ )
FK ⇒ FK − NkBT ln(T / θ )
GK ⇒ GK − NkBT ln(T / θ )
SK ⇒ SK + NkB [1+ ln(T / θ )]
..at high T
EK ⇒ EK + NkBT
#T &
µrot (T ) ≈ −kBT ln % ( H K ⇒ H K + NkBT
$θ '
C VK ⇒ C VK + NkB
!2
θ= C Kp ⇒ C Kp + NkB
2IkB
 Ideal gases: rotational contribution
Nuclear spin statistics matters! H2
1
s p = ⇒ F = 0, 1
2
antisymmetric symmetric

ortho para J = 0, 1, 2, 3, 4, ..
para: even J ★ F=0 ortho: odd J ★ F=1

ztot = 1× ∑ (2J +1)e− β EJ + 3× ∑ (2J +1)e− β EJ = 4 × ( ge ze + go zo )

J even J odd

zrot zrot z spin

spin weights
at high T.. ze ≈ zo ≈ ⇒ ztot = 4 ×
2 2 1/4 , 3/4
 Ideal gases: rotational contribution
Nuclear spin statistics matters! D2
sd = 1 ⇒ F = 0, 1, 2

antisymmetric symmetric

ortho para J = 0, 1, 2, 3, 4, ..
ortho: even J ★ F=0,2 para: odd J ★ F=1

ztot = 6 × ∑ (2J +1)e− β EJ + 3× ∑ (2J +1)e− β EJ = 9 × ( ge ze + go zo )

J even J odd

zrot zrot z spin

spin weights
at high T.. ze ≈ zo ≈ ⇒ ztot = 9 ×
2 2 2/3 , 1/3
 Ideal gases: rotational contribution
Nuclear spin statistics matters! H2
Nuclear spin conversion is difficult..
partial equilibrium
ortho para
 Ideal gases: rotational contribution
Non-linear molecules, Nrot=3

J A2 J B2 JC2
h= + +
2I A 2I B 2I C
N
I ij = ∑ mα xαi xαj i, j = x, y, z ⇒ I A , I B , I C
α =1

No analytical expression except

for spherical and symmetric-
at high enough T.. top rotors..
E 2 ∞ J A2
dφ dJ −
k BT 8π −
2 I A k BT 8π 2 3/2 1/2
zrot ≈ ∫ h 3
e = 3 × ∫ dJ A e
h
×.. = 3 × ( 2π kBT ) × ( I A I B I C )
h
−∞
3/2
! 2 "T %
θ= , I = (π I A I B I C )
1/3
z ≈$ '
2IkB #θ &
 Ideal gases: rotational contribution
Non-linear molecules, Nrot=3
J A2 J B2 JC2
h= + +
2I A 2I B 2I C

spherical rotors symmetric rotors asymmetric rotors

oblate prolate
 Ideal gases: rotational contribution
Non-linear molecules, Nrot=3

µ K ⇒ µ K − 3 kBT ln(T / θ )
2
FK ⇒ FK − 3 NkBT ln(T / θ )
2
GK ⇒ GK − 3 NkBT ln(T / θ )
2
SK ⇒ SK + 3 NkB [1+ ln(T / θ )]
2
..at high T
EK ⇒ EK + 3 NkBT
3 #T & 2
µrot (T ) ≈ − kBT ln % ( H K ⇒ H K + 3 NkBT
2 $θ ' 2
C VK ⇒ C VK + 3 NkB
!2 1/3 2
θ= , I = (π I A I B I C )
2IkB C Kp ⇒ C Kp + 3 NkB
2
 Ideal gases: rotational contribution
N
Linear molecules, Nrot=2 I = ∑ mα dα2
α =1

Non-linear molecules, Nrot=3 I = (π I A I B IC )

1/3

..at low T
σ =2 σ = 12 sum over discrete energy levels and take nuclear
spin symmetry into account
..at high T
N rot
1 !T $ 2 !2
σ = 12 σ = 60 zrot = # & ,θ =
σ "θ % 2IkB
N rot #T &
symmetry number µrot (T ) ≈ − kBT ln % ( + kBT ln σ
order of the rotational sub-group of 2 $θ '
the molecular point group of
symmetry N rot V N rot
Erot (T ) ≈ kBT, C rot = kB
2 2
 Ideal gases: rotational contribution

C5 C3 C2

E +12C5 +12C 25 + 20C3 +15C2 C2

E + 8C3 + 3C2

C3
Not always easy to
determine the
Remark symmetry number
 Ideal gases: rotational contribution

𝜎 = 12

𝜎=6

Need the correct

Remark symmetry group!
 Ideal gases: vibrational contribution
Linear molecules, Nvib=3N-5
Non-linear molecules, Nvib=3N-6
p 2k 1
h≈∑ + ∑ xkVkl xl
k 2mk 2 k,l normal modes of vibrations
# P 2k mk Ω2k 2 &
h ≈ ∑ hk = ∑% + Qk (
k k $ 2mk 2 '
N vib
N vib
zvib ≈ ∏ k=1 zvib,k , µ vib = ∑ µ vib,k
k=1
In the harmonic approximation, for each k..

− β !Ωk /2 − β !Ωk −1 !Ωk

!Ωk zvib,k = e (1− e ) , µ vib,k = + kBT ln (1− e− β !Ωk )
θk = 2
kB
 Ideal gases: vibrational contribution
Linear molecules, Nvib=3N-5
Non-linear molecules, Nvib=3N-6
p 2k 1
h≈∑ + ∑ xkVkl xl
k 2mk 2 k,l normal modes of vibrations
# P 2k mk Ω2k 2 &
h ≈ ∑ hk = ∑% + Qk (
k k $ 2mk 2 '

Some numbers..
6.62 ×10 −34 Js × 3.0 ×108 ms −1 ×10 5 m −1
ν = 1000 cm −1 ⇒ θ0 = −23 −1
= 1439.1K
1.38 ×10 JK
!Ωk hcν k H2O: θ1 ≈ 1.595θ 0 = 2295.4K θ 2 ≈ 3.656θ 0 = 5261.0K
θk = = θ 3 ≈ 3.756θ 0 = 5405.2K
kB kB
 Ideal gases: vibrational contribution
Linear molecules, Nvib=3N-5
Non-linear molecules, Nvib=3N-6
# P 2k mk Ω2k 2 &
h ≈ ∑ hk = ∑% + Qk (
k k $ 2mk 2 '

for each k..

!Ωk
µ vib,k = + kBT ln (1− e− β !Ωk )
2

T << θ k T >> θ k

!Ωk
θ
− k !Ωk #θk &
µ vib,k ≈ − kBTe T µ vib,k ≈ + kBT ln % (
2 2 $T '
 Ideal gases: vibrational contribution
Linear molecules, Nvib=3N-5
Non-linear molecules, Nvib=3N-6
# P 2k mk Ω2k 2 &
h ≈ ∑ hk = ∑% + Qk (
k k $ 2mk 2 '

for each k..

!Ωk
µ vib,k = + kBT ln (1− e− β !Ωk )
2
T << θ k T >> θ k
θk
−
Evib,k ≈ Nε 0k + NkBθ k e T
Evib,k ≈ Nε 0k + NkBT
θ
V NkBθ 2 − Tk C Vvib,k ≈ NkB
C vib,k ≈ 2
e
T
 Ideal gases: vibrational contribution
V Einstein model for vibrations in solids
C vib,k ≈ NkB
Ωk ≈ ΩE for any k

2 θk
NkBθ −
C Vvib,k ≈ 2
e T
T
 Classical equipartition theorem
Theo. The classical, equilibrium average energy of any separable,
quadratic term in the Hamiltonian is ½ kBT.

Proof. H (x, y) = ax 2 + H '(y) ⇒ Z = zZ '

where
+∞ − β ax 2 1 +∞ −t 2 π
z= ∫ −∞
dxe =
βa
∫ −∞
dte =
βa

+∞ 2 − β ax 2
2
Z' ∫ dxax e ∂ 1 k BT
ax ≡ −∞
+∞
=− ln z ≡ =
− β ax 2 ∂β 2β 2
Z' ∫ dxe
−∞

px2 J A2 1
e.g. h = , , mω 2 x 2 ,..
2m 2I A 2
Remark
 Classical equipartition theorem
Theo. The classical, equilibrium average energy of any separable,
quadratic term in the Hamiltonian is ½ kBT.

Free-particle

Harmonic Oscillator

Remark
Ideal gases: electronic contribution
Non-trivial only for systems with degenerate or
quasi-degenerate ground-states

e.g. NO is in a P state (gl = 2) with an

unpaired electron (gs = 2)
possible projections of
the total electronic 1 3 1
angular momentum along
Λ = 1, S = ⇒K = ,
the molecular axis 2 2 2
2
degeneracy is lifted by SO
coupling (ca. 15 meV)
Π1/2 , 2 Π3/2

−
Eel
−
Eel $ −
ΔE '
k BT
zel = e z el0 = e k BT
& 2 + 2 × e k BT )
& )
% (

µel = Eel − kBT ln z el0

Ideal gases: summing up all contributions

energy is used to dissociate molecule

rather than raising T

separated atoms

vibrations
V R
c (T = ∞) = nk ×
k
2
rotations

number of quadratic terms in Hk

 Ideal gases: sample exercises
Calculate the standard molar entropy of N2(g) at 10, 100 and 300 K from its
rotational constant and its vibrational wavenumber.
B! / cm −1 = 1.9987 ν! / cm −1 = 2358

# ∂F & NkBT
∅
S = − % ( = SK − N µ 'int N ≡ NA V ≡V = ∅
$ ∂T 'V ,N p

⎛ T ⎞ ⎛ !ω ⎞
⎛ Ve 5/2 ⎞ !ω −
SK = kB N ln ⎜⎜ ⎟
3 ⎟
µ R (T ) = −kBT ln ⎜ ⎟ µV = + kBT ln ⎜⎜1− e kBT ⎟⎟
⎝ N λβ ⎠ ⎝ 2θ R ⎠ 2 ⎝ ⎠
h !2 hcB" !ω hcν!
λβ = θR = = θV = = >> T
2π mkBT 2IkB kB kB kB
 Ideal gases: sample exercises
The NO molecule has a doubly degenerate electronic ground state and a doubly
degenerate first excited state at 121.1 cm-1. Calculate the electronic
contribution to the molar heat capacity and to the molar entropy of the
molecule at 100, 300 and 500 K.

µel = −kBT ln z el0 z el0 = 2 + 2 × e−E1 /kBT

N ≡ NA

C Vel = −NT µ ''int

Sel = −N µ 'int

Note: E = hcE!
 Ideal gases: sample exercises
The H2O molecule is an asymmetric C2v rotor with rotational constants
BA=27.877 cm-1, BB=14.512 cm-1 and BC=9.285 cm-1. Determine its rotational
temperature and the rotational partition function at T=0°C, 25°C and 100°C.
3/2
! 2
1/3 1 ⎛T ⎞
θ= , I = (π I A I B I C ) z≈ ⎜ ⎟
2IkB 2 ⎝θ ⎠
! 2
! ⎞
Note hcB! =
⎛!
⎜ B = ⎟
2I ⎝ 4π cI ⎠
In a given elemental solid, atoms are well approximated by three-
dimensional (3D) oscillators with vibrational wavenumbers v1=100cm-1
(doubly degenerate) and v2=200cm-1. Determine the vibrational contribution
to its molar heat capacity at T=50 K and T=300 K.
⎡ ⎛ 1⎞ ⎛ 1 ⎞⎤ 1
Em = N A ⎢2 × !ω1 ⎜ n1 (T ) + ⎟ +1× !ω 2 ⎜ n2 (T ) + ⎟⎥ nk = !ωk /kBT
⎣ ⎝ 2⎠ ⎝ 2 ⎠⎦ e −1

Note: !ω = hcν! C Vm = dEm / dT

 Real monoatomic gases
Classical partition function for N interacting atoms

1 d 3N pd 3N x − β H (x,p) 1 d 3N p − βT (p) 3N − βU (x)

Z≈
N!
∫ h 3N
e = ∫
N! h 3N
e ∫ d xe =

V N d 3N p − βT (p)
=
N! h
∫ 3N
e × Q = Z0 × Q

Ideal-gas partition function

configurational integral

1 3N − βU (x)
Q= N
V
∫d xe

F = F0 − kBT lnQ
Ideal-gas free energy “imperfections”
 Real monoatomic gases
1 3N − βU (x)
F = F0 − kBT lnQ Q= N
V
∫ d xe

" ∂lnQ %
S = S0 + kB lnQ + kBT $ '
# ∂T &V ,N
" ∂lnQ % equation of state of the
p = p0 + kBT $ '
# ∂V &T ,N real gas

2 " ∂lnQ %
E = E0 + k BT $ ' ≡ E0 +U
# ∂T &V ,N
" ∂ lnQ %
2
G = G0 + kBTV $ '
# ∂V V &T ,N
 Real monoatomic gases
1 3N − βU (x)
F = F0 − kBT lnQ Q= N
V
∫ d xe

In general, provided U is known, one just needs a high-dimensional integral

Numerics

Pros: no need to distinguish between gas, liquid and solid phases

Cons: computationally expensive

Monte Carlo methods Molecular Dynamics

 Real monoatomic gases
1 1
F = F0 − kBT lnQ, Q =
VN
∫ d 3N
xe − βU (x)
≡
VN
∫ (
d 3N
x e − βU (x)
−1) +1

keep only terms with two close atoms

(binary collisions)
N(N −1)
Q≈
2V N ∫ 3N
d x e (
− β u( 2 ) (x1,x 2 )
)
−1 +1 = f +1
pair potential can only depend on the relative position (distance):
(2)
u (x1, x 2 ) = u(x 2 − x1 ) ≡ u(r)
N2 N 2

( )
(2)
f≈
2V 2
d 3
∫ 1 2x d 3
x e − βu (x1,x 2 )
−1 =
2V
∫ (
d 3
r e − β u(r)
−1)

N 2 k BT
F = F0 − kBT ln (1+ f ) ≈ F0 − kBTf = F0 −
2V
∫ (
d 3
r e − β u(r)
−1)

Further information
 Real monoatomic gases
N 2 k BT
F = F0 − kBT ln (1+ f ) ≈ F0 − kBTf = F0 −
2V
∫ (
d 3
r e − β u(r)
−1)

N 2 k BT 1 ∞
p ≈ p0 +
V 2
B(T ) B(T ) = −
2
∫ (
d 3
r e − β u(r)
−1) ≡ −2 π ∫ (
drr 2
e − β u(r )
−1)
0

p N
≈ 1+ B(T ) +.. virial expansion
p0 V
Further information
 Real monoatomic gases

∞
B(T ) = −2π ∫ drr 2 ( e− βu(r ) −1)
0
− β u(r )
e −1 ≤ 0 e− βu(r ) −1 ≥ 0

p N
positive contribution ≈ 1+ B(T ) +.. negative contribution
p0 V
Further information
 Real monoatomic gases

R* ∞
b = −2π ∫ drr ( e
2 − β u(r )
−1) ≥ 0 a = 2π kBT ∫ drr 2 ( e− βu(r ) −1) ≥ 0
0 R*
R* ∞
2π R *3
2
b ≈ 2π ∫ drr = a ≈ 2π ∫ drr 2 u(r)
0 3 R*
..kind of volume ..strength of attraction
𝑁 P𝑘= 𝑇 𝑁P 𝑁P 𝑁𝑏
𝐹 ≈ 𝐹O + 𝑏− 𝑎 ≈ 𝐹O − 𝑎 − 𝑁𝑘= 𝑇ln 1 −
𝑉 𝑉 𝑉 𝑉
Further information
 Real monoatomic gases

R* ∞
b = −2π ∫ drr ( e
2 − β u(r )
−1) ≥ 0 a = 2π kBT ∫ drr 2 ( e− βu(r ) −1) ≥ 0
0 R*
R* ∞
2π R *3
2
b ≈ 2π ∫ drr = a ≈ 2π ∫ drr 2 u(r)
0 3 R*
..kind of volume ! N 2 $ NkBT ..strength of attraction
# p + 2 a& =
" V % V − Nb
Further information
 Real monoatomic gases

“vdW equation of state”

(1873)

..kind of volume ! N 2 $ NkBT ..strength of attraction

# p + 2 a& =
" V % V − Nb
Further information
Chemical equilibrium

ν A A + ν B B +... → ..ν X X + ν Y Y

dnA = −ν A dζ ...
dnB = −ν B dζ dnX = ν X dζ
... dnY = ν Y dζ

Gibbs free energy is at a minimum

for constant T,p

produtcs reagents
Δµ reac = ∑ ν PµP − ∑ ν Rµ R = 0
P R
 Chemical equilibrium
Equilibrium pressures
referenced to the ν A A + ν B B +... → ..ν X X + ν Y Y
standard value
dnA = −ν A dζ ...
dnB = −ν B dζ dnX = ν X dζ
... dnY = ν Y dζ

Gibbs free energy is at a minimum

for constant T,p
..for an ideal gas
" pi % " p∅ % " pi % ∅ pi
µi = kBT ln $ ∅ ' + kBT ln $ ' + µ int,i (T ) ≡ kBT ln $ ∅ ' + µ i pi = ∅
#p & # ξ i (T ) & #p & p
# ( p )νX
( p )νY &
.. ∅
Δµ = Δµ ∅ + kBT ln % X ν A Y ν B ( = 0 Δµ = −kBT ln K
$ ( pA ) ( pB ) .. '
 Chemical equilibrium
Molar translational
partition function ν A A + ν B B +... → ..ν X X + ν Y Y
electronic energy
dnA = −ν A dζ ...
dnB = −ν B dζ dnX = ν X dζ
ZPE
... dnY = ν Y dζ

Gibbs free energy is at a minimum

∅ 0
# V ∅ &
int
for constant T,p
m
µ i = Ei + ε i − kBT ln % 3(
− kBT ln z 0,i Internal partition function*
N λ
$ A i'
ΔE0 ∅ νX ∅ νY
∅
" V % int
∅
m
−
k BT (z ) (z ) ..
X Y
zi = $ 3'
× z 0,i K =e ×
# N Aλ i & ∅ νA
(z ) (z ) .. ∅ νB
A B
*referenced to ground-state energy
 Chemical equilibrium
Molar translational
partition function 𝐂𝐇𝟑 𝐂𝐥 + 𝐅 → 𝐂𝐇𝟑 𝐅 + 𝐂𝐥
electronic energy

ZPE

𝑚] , 𝑚^ , 𝑚^_ , 𝑚` ,
𝐷b^^_ , 𝐷b^`
# ∅ & ^] d ^_ ^] d `
V 𝜔5 , 𝜔5
µ i∅= Ei + ε i0 − kBT ln % m 3 ( − kBT ln z int
0,i ^] d ^_ ^] d ^_ ^] d ` ^] d ^`
N λ
$ A i' 𝐼∥ , 𝐼f , 𝐼∥ , 𝐼f
Internal partition function*
ΔE0 ∅ νX ∅ νY
∅
" V % int
∅
m
−
k BT (z ) (z ) ..
X Y
zi = $ 3'
× z 0,i K =e ×
# N Aλ i & ∅ νA
(z ) (z ) .. ∅ νB
A B
*referenced to ground-state energy
 Chemical equilibrium
Equilibrium fugacities
referenced to the ν A A + ν B B +... → ..ν X X + ν Y Y
standard value
dnA = −ν A dζ ...
Ideal gas chemical
potential dnB = −ν B dζ dnX = ν X dζ
... dnY = ν Y dζ

Note: for a single component real gas

..for a real gas 2 B(T )(n−n∅ )
f / p≡φ ≈ e
⎛ fi ⎞ ∅ fi
µi ≡ kBT ln ⎜ ∅ ⎟ + µi fi =
⎝p ⎠ p∅ ∅
Δµ = −kBT ln K
# ( f )νX
( f )νY &
..
Δµ = Δµ ∅ + kBT ln % X ν A Y ν B ( = 0 ∅ ..as above
$ ( f A ) ( fB ) .. ' Δµ
Chemical equilibrium

H 2 → 2H

De = 4.748 eV = 458.11 kj / mol

re = 74 pm = 1.401 a0
ν e = 4401.2 cm −1

θ H 2 = 87.9K
hcν e
ε0 = = 0.273 eV
2
ΔE0 ≡ D0 = (4.748 − 0.273) eV = 4.475 eV

kBT hcν e ΔE0

we need.. λH 2 , λH , ∅
, ,
p k BT k BT
 Chemical equilibrium electron spin
electronics ΔE0 3 2
−
k BT λ 2
K =e k BT
× ∅ × H6 2 ×
p λH 1 %T ( % hcν e (−1
−
k BT
' * ' × '1− e *
translations
2 & θ ) * vibrations
@298.15K symmetry & )
hcν e rotations
λH 2 = 71.2 pm, λH = 100.7pm = 21.24
k BT k BT
∅ 10 3
= v = 4.11×10 pm K = 8.39 ×10 −72
p∅ ΔE0
= 174.08
T / θ H 2 = 3.392 k BT

@2981.5K
λH 2 = 22.2 pm, λH = 31.8pm hcν e
= 2.124
k BT k BT
∅ 11 3
= v = 4.11×10 pm K = 2.46 ×10 −2
p∅ ΔE0
= 17.41
T / θ H 2 = 33.92 k BT
 Chemical equilibrium
1 p 2H p x 2H ni
K= ∅× ≡ ∅× xi =
p pH 2 p xH2 nH 2 + nH

H 2 → 2H
N(1− α ) 2Nα

xH =
2α
xH2 =
1− α p 4α 2 p∅ K
K= ∅× α=
1+ α 1+ α p 1− α 2 4 p + p∅ K

Even diffuse interstellar

clouds are 10-18
p∅ p∅
@298.15K K = 8.39 ×10 −72
α≈
1
K = 1.43×10 −36
p >> 10 −72 p∅ (!!)
2 p p

$
& 0.0784 / p / p∅ p >> 6 ×10 −3 p∅
@2981.5K K = 2.46 ×10 −2 α =%
&' 1 p << 6 ×10 −3 p∅
 Frequently Asked Questions

General

• Boltzmann distribution and partition function

• Statistical formulation of thermodynamics
• Entropy and temperature
• Ideal molecular gases
• Real gases
• Chemical equilibrium in statistical mechanics
• Thermodynamic potentials from statistical mechanics
 Frequently Asked Questions

Boltzmann distribution

1. a) Determine the average potential energy V for a classical harmonic

oscillator in thermal equilibrium with a reservoir at a temperature T. b)
Noticing that V = 1 / 2mω 2 x 2 determine the average quadratic displacement of the
harmonic oscillator as a function of T.

1. a) The quantum virial theorem for a harmonic oscillator states that

1 !ω " 1 %
V n ≡ ψ n V ψ n = T n = En = $n + '
2 2 # 2&
(where V, T and E are the potential, kinetic and total energy, respectively). Use
it to find the average potential energy of a quantum harmonic oscillator in
equilibrium with a reservoir at a temperature T. b) Noticing that V = 1 / 2mω 2 x 2
determine the average quadratic displacement of the harmonic oscillator as a
function of T.
 Frequently Asked Questions

Boltzmann distribution

3. a) The energy of a rigid dipole µ in an electric field E0 is given by H = −µ E0 cosθ ,

where q is the istantaneous angle between the two vectors. Using classical
statistical mechanics determine the probability of finding the dipole at a given
angle when the system is in thermal equilibrium at a temperature T. Hint: put
E0 along z and use the two spherical angles of a polar coordinate reference
system to identify each dipole configuration. b) Determine the average dipole
moment <µ> at high enough temperatures that kBT>>µE0.

4. a) Determine the probability distribution of the coordinate of a classical

harmonic oscillator in equilibrium with a reservoir at a temperature T.

5. a) Determine the probability distribution of the velocity v of a classical atom in

equilibrium at a temperature T. a) Determine the probability distribution of the
magnitude v of v.
 Frequently Asked Questions

Partition functions

1. Calculate the thermal wavelength and the translational partition function at (i)
300 K and (ii) 3000 K of a molecule of molar mass 150 g mol−1 in a container of
volume 1.00 cm3.

2. a) The bond length of O2 is 120.75 pm. Use the high-temperature

approximation to calculate the rotational partition function of the molecule at
300 K. b) Same for N2 (bond length 109.75 pm).

1. Give the symmetry number for each of the following molecules: (a) CO2, (b) O3,
(c) SO3, (d) SF6, (e) Al2Cl6, (f) CO, (g) O2, (h) H2S, (i) SiH4, and (l) CHCl3.

2. a) The vibrational wavenumber of Br2 is 323.2 cm−1. Evaluate the vibrational

partition function explicitly (without approximations). b) The same for I2 (214.5
cm-1).
 Frequently Asked Questions

Partition functions

5. Calculate the vibrational partition function of HCN at 900K given the

wavenumbers 3311 cm−1 (symmetric stretch), 712 cm−1 (bend; two modes), and
2097 cm−1 (asymmetric stretch).

6. Calculate the vibrational partition function of CCl4 at 500K given the

wavenumbers 459 cm−1 (symmetric stretch, A), 217 cm−1 (deformation, E), 776
cm−1 (deformation, T), and 314 cm−1 (deformation, T).

7. The four lowest electronic levels of a Ti atom are: 3F2,3F3,3F4, and5F1,

at 0, 170, 387, and 6557 cm−1, respectively. There are many other electronic
states at higher energies. The boiling point of titanium is 3287°C. What are the
relative populations of these levels at the boiling point? Hint: The term symbols
stand for 2S+1LJ and the degeneracies of the levels are 2J + 1.
 Frequently Asked Questions

Thermodynamics
1. a) Calculate the standard molar entropy of neon gas at (a) 200 K, (b) 298.15 K.
b) The same for Xenon.

2. The variation of the atmospheric pressure p with altitude h is predicted by the

barometric formula to be p = p0 e(−h/H) where p0 is the pressure at sea level
and H = RT/Mg with M the average molar mass of air and T the average
temperature. Compare the relative number densities, n (h)/n (0),
for O2, N2 and H2O at h = 8.0 km.

3. A CO2 molecule is linear, and its vibrational wavenumbers are 1388.2 cm−1,
2349.2 cm−1, and 667.4 cm−1, the last being doubly degenerate and the others
nondegenerate. The rotational constant of the molecule is 0.3902 cm−1.
Calculate the rotational and vibrational contributions to the molar Gibbs energy
at 298 K.
 Frequently Asked Questions

Thermodynamics
4. An O3 molecule is angular, and its vibrational wavenumbers are 1110 cm−1, 705
cm−1, and 1042 cm−1. The rotational constants of the molecule are 3.553 cm−1,
0.4452 cm−1, and 0.3948 cm−1. Calculate the rotational and vibrational
contributions to the molar Gibbs energy at 298 K .

5. Calculate the equilibrium constant of the reaction I2(g) -> 2 I(g) at 1000 K from
the following data for I2: n = 214.36 cm−1, B = 0.0373 cm−1, De = 1.5422 eV. The
ground state of the I atoms is 2P3/2, implying fourfold degeneracy.

6. The energy levels of a CH3 group attached to a larger fragment are given by the
expression for a particle on a ring, provided the group is rotating freely. What is
the high-temperature contribution to the heat capacity and entropy of such a
freely rotating group at 25°C? The moment of inertia of CH3 about its threefold
rotation axis (the axis that passes through the C atom and the centre of the
equilateral triangle formed by the H atoms) is 5.341 × 10−47 kg m2.
 Frequently Asked Questions

Thermodynamics
7. The free electrons in a semiconductor behave like a classical ideal gas, with a
given effective mass mC. In a given semiconductor mC = 0.04 me; determine
their chemical potential, their entropy per unit volume and their specific heat
per unit volume when T = 300 K and the number of e per unit volume (ne) is
1016 cm-3.
8. Creation of free electrons (e) and holes (h) in a semiconductor is described by
a chemical reaction O → e + h where O is the structureless vacuum state (i.e.
ZO ≡ 1), e and h are classical ideal gases with masses mC and mV and the
reaction (dissociation) energy is the gap energy Egap. Given that Egap = 0.66 eV,
mC = 0.04 me and mV = 0.28 me determine i) the equilibrium constant in terms
of concentrations and ii) the equilibrium concentration of electrons and
holes (ne, nh) at T = 300 and T =400 K.
 Frequently Asked Questions
Solution to Problem 8

∆𝜇t = 𝜇b + 𝜇u + 𝐸v = 0 since we can put 𝜇w ≡ −𝐸v

𝜇b = 𝑘= 𝑇𝑙𝑛 𝑛b 𝑣Bb − 𝑘= 𝑇𝑙𝑛𝑔b where 𝑔b = 2 is due to the e spin

𝜇u = 𝑘= 𝑇𝑙𝑛 𝑛u 𝑣Bu − 𝑘= 𝑇𝑙𝑛𝑔u where 𝑔u = 2 is due to the h spin
Hence
𝑛b 𝑛u 𝑣Bb 𝑣Bu
𝑘= 𝑇𝑙𝑛 + 𝐸v = 0
𝑔b 𝑔u
or equivalently
C}
A
{=𝑒
𝑛b 𝑛u = 𝐾 ,7~ 𝑁 𝑁
b u
where for X=e,h
„/P
• A€ 2𝜋𝑚•∗ 𝑘= 𝑇
𝑁• = 𝑔• 𝑣B = 𝑔•
ℎP

Note: 𝑚•∗ are the effective masses, 𝑚b∗ = 𝑚† and 𝑚u∗ = 𝑚‡

 Frequently Asked Questions

Thermodynamics
9. Compute the degree of dissociation of the 7Li dimer at 300 K under standard
conditions, upon determining the equilibrium constant of the reaction Li2(g)
Š = 0.4975 cm-1, De
→ 2Li(g) from the following data for 7Li2: v̂ = 351.43 cm-1, B
= 1.03 eV (the ground-state of the Li atoms is 2S1/2, that is doubly
degenerate, and the atomic mass of the 7Li isotope is 7.016 amu).
10. Calculate the equilibrium constant at (a) 298 K and (b) 800 K for the gas-
phase exchange reaction H2O + DCl ⟶ HDO + HCl from the following data
(Note: hcv̂ = ℏω)

Molecule ˆ cm-1
𝑣/ 𝐵‘ A / cm-1 𝐵‘ B / cm-1 𝐵‘ C / cm-1
H2O 3656.7, 1594.8, 3755.8 27.88 14.51 9.29
HDO 2726.7, 1402.3, 3707.5 23.38 9.102 6.417
HCl 2991 10.59
DCl 2145 5.499
 Frequently Asked Questions

Thermodynamics
12. Calculate the degree of ionization of atomic hydrogen in thermal equilibrium
at T = 300 K and T = 2000 K, given that the ionization energy (H → e- + H+) is
13.59844 eV. Note: the first four excited states of H lie 10.19988 eV above
the ground-state and are not appreciably populated at the given
temperatures.