Lagrangian Dynamics Problems

Monatomic ideal gas: partition
Faculty of Science, Charles University in Prague

http://www.natur.cuni.cz/chemie/fyzchem
functions and equation of state.

Peter Košovan
peter.kosovan@natur.cuni.cz
Dept. of Physical and Macromolecular Chemistry
Statistical Thermodynamics, MC260P105, Lecture 3, 27.10.2014
If you find a mistake, kindly report it to the author :-)

Systems of non-interacting particles
For non-interacting particles a, b, c, d, . . . we can decompose the

system Hamiltonian to individual contributions:
Ĥ ≈ Ĥ a + Ĥ b + Ĥ c + Ĥ d + . . .
Consequently, the energy is a sum of individual particle energies
E ≈ εa + εb + εc + εd + . . .
• Complex multi-body problem approximated as a superposition of
simpler one- and two-body problems.
• Often encountered in Physics
• Allows for systematic corrections
• e. g. Separation of a single molecule Hamiltonian
Ĥ ≈ Ĥtranslation + Ĥrotation + Ĥvibration + Ĥelectronic + Ĥnuclear + . . .
ε ≈ εtranslation + εrotation + εvibration + εelectronic + εnuclear + . . .

P. Košovan Lecture 3: Monatomic ideal gas 1/24
Systems of non-interacting particles
Suppose we can decompose Hamiltonian to individual contributions.

Non-interacting distinguishable particles a, b, c, . . . :
a b c
X X
Q(N, V , T ) = e−βEj = e−β(εk +εl +εm +... )
j k ,l,m,...
X X X
−βεak −βεbl −βεcm
= e e e · · · = qa qb qc . . .
k l m
where k , l, m, . . . are indices of quantum states of particles a, b, c, . . .

Single-particle partition function:
i
e−βεj
X
qi (V , T ) =
j

Distinguishable vs. indistinguishable particles

• If all particles are the same but distinguishable, qa = qb = qc = q :
a b c
X
Q(N, V , T ) = e−β(εk +εl +εm +... ) = qa qb qc · · · = q N (V , T )
k ,l,m,...
• The N-body problem reduces to a one-body problem!

Distinguishable vs. indistinguishable particles

• If all particles are the same but distinguishable, qa = qb = qc = q :
a b c
X
Q(N, V , T ) = e−β(εk +εl +εm +... ) = qa qb qc · · · = q N (V , T )
k ,l,m,...
• The N-body problem reduces to a one-body problem!

• But identical particles are indistinguishable:
X
Q(N, V , T ) = e−β(εk +εl +εm +... )
k ,l,m,...
• Permutation of k and l yields the same quantum state of the system.

• Correct for double-counting: N! permutations.

Indistinguishable particles
• For indistinguishable particles:

q N (V , T )
X
Q(N, V , T ) = where q(V , T ) = e−βεj
N!
j


q N (V , T )
X
N!
j
• We silently ignored multiply occupied states: εi = εj :


q N (V , T )
X
N!
j

• Bosons: ψ symmetric with respect to permutation
⇒ any number of particles can occupy a given quantum state.


q N (V , T )
X
N!
j

• Fermions: ψ antisymmetric with respect to perumtation
⇒ two particles cannot occupy the same quantum state.


q N (V , T )
X
N!
j

• Fermions: ψ antisymmetric with respect to perumtation
⇒ two particles cannot occupy the same quantum state.
• We will see that except for low temperatures or high densities the
number of states N N.
• Then multiply occupied states are rare and the equation above is an
excellent approximation
Some useful results from quantum mechanics (QM)
Time-independent Schrödinger equation: 7

6
Ĥψ = Eψ 5
4
ny
Particle in a well of length a: 3
2
h2 ∂ 2 1
Ĥ = − 0
2m ∂x 2 0 1 2 3 4 5 6 7
nx
h2 n2
εn = n = 1, 2, . . . Number of states with εnx ,ny ,nz < ε:
8ma2
1 4πR 3

Particle in a 3d box of length a: Φ(ε) =
8 3
h2
π 8ma2 ε 3/2

εnx ,ny ,nz = (n2 + ny2 + nz2 )
8ma2 x ... =
6 h2
Degeneracy of translational energy levels
Density of energy levels from previous slide:

π 8ma2 ε 3/2

Φ(ε) =
6 h2
Number of levels between ε and (ε + ∆ε):
π 8ma2 3/2 1/2

2
ω(ε, ∆ε) = Φ(ε + ∆ε) − Φ(ε) = ε ∆ε + O (∆ε)
4 h2
Let’s plug in some numbers:

ε = 3kB T /2, T = 300 K, m = 10−22 g, a = 10 cm, ∆ε/ε = 0.01:
ω(ε, ∆ε) ≈ O(1028 )
Degeneracy of translational energy levels far exceeds number of

particles at sufficiently low density and high temperature.
Fermi-Dirac and Bose-Einstein statistics
• Sometimes we have to explicitly account for

multiple occupancy of quantum states
• At low T and high density

• Partition function in terms of molecular *Constrained sum:
energy levels (occupation numbers nk ): X
N= nk
X X∗ P k
Q(N, V , T ) = e−βEj = e−β i εi ni
X
j {nk } Ej = εk nk
k
• Evaluation of the restricted sum is awkward.
• Convenient solution: grandcanonical ensemble (GCE).

Formulation in GCE: Absolute activity:

∞
X λ = eβµ
Ξ(µ, V , T ) = eβµN Q(N, V , T )
N=0
µ = kB T ln λ
Rearrangements (* is the restricted sum from the previous slide):
∞ X∗ ∞ X P
X P X ∗ P
Ξ(µ, V , T ) = λN e−β i εi ni = λ i ni e−β i εi ni
N=0 {nk } N=0 {nk }
X∞ X ∗ Y nk
= λe−βεk
N=0 {nk } k
Crucial step (now each nk ranges over all possible values):

n1max max
X nX
2 Y n k
Ξ(µ, V , T ) = ··· λe−βεk
n1 =0 n2 =0 k
We continue rearranging
n1max n2max

X X Y nk
λe−βεk
Ξ(µ, V , T ) = ···
n1 =0 n2 =0 k
n1max n1 nX
2
max
n2
X
−βε1
= λe λe−βε2
n1 =0 n2 =0
nkmax nk
YX
= λe−βεk
k nk =0
Last equation is a general result. Special cases:

Fermions, nkmax = 1: Bosons, nkmax = ∞:
∞ nk
Y YX
ΞFD = 1 + λe−βεk ΞBE = λe−βεk
k k nk =0
P∞
Use j=0 x
j = (1 − x)−1 for x < 1 to rewrite BE formula

∞ nk Y −1
YX
ΞBE = λe−βεk = 1 − λe−βεk for λe−βεk < 1
k nk =0 k
and cast both FD and BE formula in the same form

Y ±1
Ξ FD = 1 ± λe−βεk for λe−βεk < 1
BE
k
• These are the only exact distributions in statmech.

• Low T and high density: FD or BE statistics apply, q(N, V , T ) has no
meaning (symmetry requirements of the wave function)
• High T and low density: both degenerate to Boltzmann statistics
• Nobel prize in Physics 2001: experiment Bose-Einstein condensate.
Thermodynamic quantities from FD and BE statistics
Number of particles: Number of particles
in state k :

X ∂ ln Ξ
N=N= n k = kB T
∂µ λe−βεk
k V ,T nk =
X λe−βεk 1 ± λe−βεk
∂ ln Ξ
=λ =
∂λ V ,T 1 ± λe−βεk
k
Energy E and average energy per particle, ε:

X X λεk e−βεk
E = Nε = n k εk =
1 ± λe−βεk
k k
X
pV = kB T ln Ξ = ±kB T ln 1 ± λe−βεk
k

The limiting case of Boltzmann
For λ 1 (equivalent βµ 0):

λe−βεk
nk =
1 ± λe−βεk
we can write approximate relations
X X
nk = λe−βεk , N = nk = λ e−βεk
k k
e−βεk
P
and using q(N, V , T ) = k
nk e−βεk e−βεk
= P −βε =
N ke
k q(N, V , T )
i. e. both FD and BE reduce to Boltzmann statistics.

The limiting case of Boltzmann
Similarly, for small λ we obtain:

εj e−βεj
P
X λεk e−βεk X E j
E= → λεj e−βεj , ε= P → P
−βε
1 ± λe k nk e−βεj
k j k j
Using ln(1 + x) ≈ x for small x:

X X
pV = kB T ln Ξ → ±kB T ±λ e−βεj = λkB T e−βεj = λkB Tq

j j
so that
βpV = ln Ξ = λq
∞ ∞
X (λq)N X qN
Ξ = eλq = = λN Q(N, V , T ), where Q(N, V , T ) =
N! N!
N=0 N=0

Ideal monatomic gas
At high temperature and low
pressure (Boltmzmann limit):

q N (V , T )
Q(N, V , T ) =
N!
Further decomposition of q:
q(V , T ) = qtr qel qnucl
Nuclear partition function:
qnucl = ωn1 + . . .
Except for rare cases just a

constant.

Ideal monatomic gas
At high temperature and low Electronic partition function:
pressure (Boltmzmann limit):

qelec = ωe1 + ωe2 e−β∆ε1,2 + . . .
q N (V , T )
Q(N, V , T ) =
N!
• Zero energy at electronic
Further decomposition of q:
ground state
q(V , T ) = qtr qel qnucl • Can be degenerate
Nuclear partition function: • Higher excited states typically

several eV
qnucl = ωn1 + . . . • At 300 K 1eV ≈ 40 kB T
Except for rare cases just a • First two or three terms

constant. usually suffice

Quantitative view of electronic levels

Table from McQuarrie, Statistical Mechanics, University Science Books (2000)

Quantitative view of electronic levels
Fraction of electrons in second excited state:

ωe2 e−β∆ε1,2
f2 =
ωe1 + ωe2 e−β∆ε1,2 + . . .
Higher electronic states need to be considered at higher temperatures.

Translational partition function
Translational energy levels:
h2

εnx ,ny ,nz = (n2 + ny2 + nz2 ), nx , ny , nz = 1, 2, . . .
8ma2 x
∞
X
qtr = e−βεnx ,ny ,nz
nx ,ny ,nz =1
∞ ∞ ∞
−βh2 nx2 −βh2 nx2 X −βh2 nx2
X X
= exp exp exp
8ma2 8ma2 8ma2
nx =1 nx =1 nx =1
∞ !3 Z ∞ !3
−βh2 n2 −βh2 n2
X
= exp ≈ exp dn
8ma2 n=0 8ma2
n=1
Alternative approach
∞ ∞
π 8ma2 3/2 ∞ 1/2 −βε
X Z Z
−βε −βε
qtr = ω(ε)e ≈ ω(ε)e dε = ε e dε
n=0 4 h2 n=0
ε=0
We evaluate
!3
∞
2πmkB T 3/2

−βh2 n2
Z
qtr = exp dn = V
n=0 8ma2 h2
and introduce thermal de Broglie wavelength Λ

1/2
h2

V
Λ= such that qtr = 3
2πmkB T Λ
Translational energy and momentum per particle:

2 ∂ ln qtr 3 h
εtr = kB T = kB T , |~p| = (3mkB T )1/2 , Λ≈
∂T 2 |~p|

We evaluate
!3
∞
2πmkB T 3/2

−βh2 n2
Z
qtr = exp dn = V
n=0 8ma2 h2
and introduce thermal de Broglie wavelength Λ

1/2
h2

V
Λ= such that qtr = 3
2πmkB T Λ
Translational energy and momentum per particle:

2 ∂ ln qtr 3 h
εtr = kB T = kB T , |~p| = (3mkB T )1/2 , Λ≈
∂T 2 |~p|
Boltzmann applies at Λ3 V , i. e. when quantum effects diminish.

Summary – single-particle partitition function
q(V , T ) = qtr qel qnu

3/2
2πmkB T V
qtr = V =
h2 λ3
qel = ωe1 + ωe2 e−β∆ε12 + . . .
qnu = ωn1 + . . .
• The above holds for particles without inernal structure

(monatomic ideal gas)
• Vibrational and rotational terms arise for composite particles
(next lecture)
Thermodynamic functions of an ideal monatomic gas

A(N, V , T ) = −kB T ln Q = kB T ln N! − NkB T ln q(V , T )
" #
2πmkB T 3/2 Ve

− NkB T ln ωe,1 + ωe,2 e−β∆ε1,2

= −NkB T ln 2
h N

2 ∂ ln Q 3 Nωe,2 ∆ε1,2
E = kB T = NkB T +
∂T N,V 2 qel
In both above cases, the first term is dominant.

∂ ln Q NkB T
p = kB T =
∂V N,T V
Equation of state (EOS) of an ideal gas.

Entropy:

∂ ln Q

S = kB T + kB ln Q
∂T N,V
" #
2πmkB T 3/2 Ve5/2

3
= NkB + NkB ln
2 h2 N
ωe,1 + ωe,2 e−β∆ε1,2

−β∆ε1,2

+ NkB ln ωe,1 + ωe,2 e + NkB
qel
Sackur-Tetrode equation:
" #
2πmkB T 3/2 Ve5/2

3
S = NkB + NkB ln + Sel
2 h2 N

Quantitative view of entropy
Sackur-Tetrode equation:
" #
2πmkB T 2/2 Ve5/2

3
S = NkB + NkB ln + Sel
2 h2 N
Higher electronic states have to be considered at higher temperatures.

Chemical potential:

∂ ln Q q
µ = −kB T = −kB T ln
∂N T ,V N
" #
2πmkB T 3/2 V

= −kB T ln − kB T ln qel qnu
h2 N
" #
2πmkB T 3/2 kB T

p
= −kB T ln 2
− kB T ln qel qnu + kB T ln
h p p
p
= µ0 (T ) + kB T ln
p
where
" 3/2 #
2πmkB T kB T
µ0 (T ) = −kB T ln − kB T ln qel qnu
h2 p

Summary
• Separation of different contributions to Ĥ, E, Q and q

• Fermi-Dirac and Bose-Einstein statistics
• Boltzmann as high-temperature and low-density limit

• Thermal wavelength
• EOS of an ideal gas from first principles (Boltzmann limit)

Summary
• Separation of different contributions to Ĥ, E, Q and q

• Fermi-Dirac and Bose-Einstein statistics
• Boltzmann as high-temperature and low-density limit

• Thermal wavelength
• EOS of an ideal gas from first principles (Boltzmann limit)
What comes next

• Polyatomic gas molecules – vibration and rotation
• Condensed matter – dense gases and liquids (classical limit)
• Distinguishable particles – crystals, magnets

Lagrangian Dynamics Problems

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Monatomic ideal gas: partition

Faculty of Science, Charles University in Prague

functions and equation of state.

Dept. of Physical and Macromolecular Chemistry

Statistical Thermodynamics, MC260P105, Lecture 3, 27.10.2014

If you find a mistake, kindly report it to the author :-)

Faculty of Science, Charles University in Prague

Ĥ ≈ Ĥtranslation + Ĥrotation + Ĥvibration + Ĥelectronic + Ĥnuclear + . . .

ε ≈ εtranslation + εrotation + εvibration + εelectronic + εnuclear + . . .

Suppose we can decompose Hamiltonian to individual contributions.

Faculty of Science, Charles University in Prague

where k , l, m, . . . are indices of quantum states of particles a, b, c, . . .

P. Košovan Lecture 3: Monatomic ideal gas 2/24

Faculty of Science, Charles University in Prague

• The N-body problem reduces to a one-body problem!

P. Košovan Lecture 3: Monatomic ideal gas 3/24

Faculty of Science, Charles University in Prague

• The N-body problem reduces to a one-body problem!

• Permutation of k and l yields the same quantum state of the system.

P. Košovan Lecture 3: Monatomic ideal gas 3/24

Faculty of Science, Charles University in Prague

P. Košovan Lecture 3: Monatomic ideal gas 4/24

Faculty of Science, Charles University in Prague

• We silently ignored multiply occupied states: εi = εj :

P. Košovan Lecture 3: Monatomic ideal gas 4/24

Faculty of Science, Charles University in Prague

• We silently ignored multiply occupied states: εi = εj :

P. Košovan Lecture 3: Monatomic ideal gas 4/24

Faculty of Science, Charles University in Prague

• We silently ignored multiply occupied states: εi = εj :

P. Košovan Lecture 3: Monatomic ideal gas 4/24

Faculty of Science, Charles University in Prague

• We silently ignored multiply occupied states: εi = εj :

Faculty of Science, Charles University in Prague

Faculty of Science, Charles University in Prague

Number of levels between ε and (ε + ∆ε):

π 8ma2 3/2 1/2

Let’s plug in some numbers:

ω(ε, ∆ε) ≈ O(1028 )

Degeneracy of translational energy levels far exceeds number of

• Sometimes we have to explicitly account for

Faculty of Science, Charles University in Prague

• At low T and high density

P. Košovan Lecture 3: Monatomic ideal gas 7/24

Faculty of Science, Charles University in Prague

Crucial step (now each nk ranges over all possible values):

Faculty of Science, Charles University in Prague

Last equation is a general result. Special cases:

Faculty of Science, Charles University in Prague

and cast both FD and BE formula in the same form

• These are the only exact distributions in statmech.

Faculty of Science, Charles University in Prague

Energy E and average energy per particle, ε:

P. Košovan Lecture 3: Monatomic ideal gas 11/24

For λ  1 (equivalent βµ  0):

Faculty of Science, Charles University in Prague

i. e. both FD and BE reduce to Boltzmann statistics.

P. Košovan Lecture 3: Monatomic ideal gas 12/24

Faculty of Science, Charles University in Prague

Using ln(1 + x) ≈ x for small x:

P. Košovan Lecture 3: Monatomic ideal gas 13/24

Faculty of Science, Charles University in Prague

q(V , T ) = qtr qel qnucl

Nuclear partition function:

For λ 1 (equivalent βµ 0):