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5.62 Physical Chemistry II

Spring 2008

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 5.62 Lecture #10: Quantum vs. Classical. qtrans.
Equipartition. Internal Degrees of Freedom.
GOAL: Calculate average translational energy via quantum and classical
descriptions and compare results.

QUANTUM DESCRIPTION — Calculate –ε

x — average kinetic energy in x-direction

∞
εx = ∫0
ε x P ( ε x ) dε x

P ( ε x ) = ( πkT)
−1/2 −1/2 −ε x
kT

εx e
1/2
⎛ 1 ⎞ ∞
1/2 −ε kT
εx = ⎜
⎝ πkT ⎟⎠ ∫0 ε x
e x dε x
1/2
⎛ 1 ⎞ kT
( πkT)1/2 = 1
kT
εx = ⎜
⎝ πkT ⎟⎠ 2 2
1
This is not an accident. It is our first glimpse of “equipartition” of energy, 2kT into each
independent degree of freedom.

Integral table for two useful integrals

π1/2
( dimension: )
∞
∫ 0
x1/2 e− ax dx =
2a 3/2
length 3/2

( dimension: )
∞
∫ x −1/2 e− ax dx = ( π a )
1/2
length1/2
0

Since the translational energies in each dimension are uncorrelated, average total energy
is the sum of the average energy in each direction. Also, as a consequence of the
separability of the Hamiltonian with respect to x, y, z coordinates, total E is sum of Ex +
E y + E z.

–ε = –
ε
+
ε

– +
ε

x y z

1
1 1 3
2kT + 2kT + 2kT = 2kT

1
Each degree of freedom contributes 2kT to total energy.

Agrees with result from ensemble average

5.62 Spring 2008 Lecture #10, Page 2

⎛ ∂ ln Q trans ⎞ 3
ε = E = kT2 ⎜ ⎟⎠ = ∑ Pα E α = kT

⎝ ∂T N,V α

CLASSICAL MECHANICAL DESCRIPTION — calculate –ε

State of a molecule is described by p momentum, q position. The energy of

~ ~
N–molecule system is ε(p 3N, q 3N), which is a continuous function of 6N variables.
~ ~

− ε( p,q )/kT
q trans = ∑ e − ε i kT
let's assume this by analogy ∫∫ e ~ ~ dp dq
~ ~
i
quantum ⇒ classical — integral over 3
momentum and 3 position
coordinates for each particle

↓= p x + p y + p z
2 2 2

∫∫∫ dq x dq y dq z ∫∫∫ dp x dp y dp z e−p / (2mkT)

2
q trans,cl =
−p 2y /2mkT
=V∫ dp x e−p x /2mkT ∫ ∫
2 2
dp y e dp z e−p z /2mkT

⎡ ∞ ⎤3
= V⎢ ∫ dp x e p x /2mkT ⎥ = V (2πmkT)
2 3/2
⎣ −∞ ⎦

[qtrans,cl. should be dimensionless, but this has units m3l6t–3 = h3]

The need to divide by a factor of h3 was recognized by Boltzmann even before Planck “invented”
h. It is impossible for a trajectory in phase space to intersect itself. [Why? Because the classical
Hamiltonian is a function of q,p. If the system is at q(t1), p(t1) at t1 then the H tells us the values
of q and p at t1 + δt. If the system returns to q(t1), p(t1) at t2, then it must move to q(t1 + δt), p(t1
+ δt) at t2 + δt.] The ergodic hypothesis requires trajectories to visit “each cell” of phase space of
volume h3N, not “each location” in phase space. This avoids the problem of self-intersecting
trajectories.
3/2
⎛ 2πmkT ⎞
Comparing to q trans,qm = ⎜ V , we see that we need a factor of h3 in the denominator
⎝ h 2 ⎟⎠
of qtrans,cl.. In fact, it turns out that to construct a partition function from a classical Hamiltonian,
this h–3 factor is required, so our assumption above must be corrected:

1
q trans,cl = 3
∫∫ e −ε classical kT
dp dq (dimensionless)
h ~ ~
3N/2
qN 1 ⎡ −ε N VN ⎛ 2πmkT ⎞
Q trans,cl = trans,cl = ⎣ ∫ ∫ e classical
kT ⎤
dp dq ⎦ = ⎜ ⎟
N! N!h 3N N! ⎝ h 2 ⎠

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5.62 Spring 2008 Lecture #10, Page 3

CONCLUSION: Classical and quantum descriptions of translational degrees of freedom yield

consistent results. QM is operating in classical limit because energies of the translational states
are so closely spaced that they can be approximated as continuous, as in classical mechanics.

kT = 0.6 kcal mol–1 at 300K

∆ε = 10 –20 kcal mol–1

(particle in box)

3
The average molecular translational energy, 2 kT, is independent of the kind of molecule, or
more precisely, independent of the energy level spacings because these spacings are ~ 1020 times
smaller than kT. Spacings don't change much from He, to C6H6, to DNA. If T were decreased to
–
10–19 K, then He, C6H6, and DNA would have different Etrans.

CLASSICAL EQUIPARTITION OF ENERGY PRINCIPLE

1
Each squared momentum or position term in the energy of a particle contributes 2 kT to the
average energy; according to this principle, translation along each coordinate axis contributes
1 1
2 kT; rotation about each principal axis contributes 2 kT; and each vibrational mode contributes
1
kT (2 kT each for kinetic and potential energy) to the average energy.

−ε (p 3N ,q 3N ) kT Classical Boltzmann
~ ~
g(ε)e distribution function
P (ε) = 3N
−ε(p ,q 3N ) kT
∫∫ d p 3N d q 3N N!h 3N
~ ~
e
~ ~
g(ε) is the density of states, often denoted as ρ(ε). It has units (energy)–1.
∞ 1 1 1 3
ε = ∫ εP ( ε ) dε = εx + εy + εz = kT + kT + kT = kT
0 2 2 2 2

INTERNAL DEGREES OF FREEDOM — FACTORIZATION OF Q

ATOMS — have one internal degree of freedom

ELECTRONIC degree of freedom

revised 2/29/08 8:52 AM

5.62 Spring 2008 Lecture #10, Page 4

MOLECULES — have other degrees of freedom

ELECTRONIC, VIBRATION, AND ROTATION, each of which contributes

to total energy and to other macroscopic properties.

Nuclear hyperfine? [Nuclear spin degeneracy factors. LATER.]

Internal energy adds to translational energy to get total energy

ε = εtrans + εint

quantum #'s internal quantum #'s

N,M,L

where εint = energy from internal degrees of freedom

q = ∑ e−εi = ∑ e ( trans int )

kT −ε +ε kT

all molecular all molecular

states states

We do not have to start over. qtrans factors out.

q = ( ∑ e −ε trans kT
)( ∑ e−ε int kT
)
translational states internal states

q= qtrans • qint ← INTERNAL MOLECULAR

PARTITION FUNCTION

Q=
( q trans q int )
N
⎛q N ⎞
= ⎜ trans ⎟ q N
N! ⎝ N! ⎠ int

Q = QtransQint CANONICAL PARTITION

FUNCTION

QN CANONICAL TRANSLATIONAL
Q trans = trans
PARTITION FUNCTION
N!

Q int = Q N CANONICAL INTERNAL

int
PARTITION FUNCTION

revised 2/29/08 8:52 AM

5.62 Spring 2008 Lecture #10, Page 5

NOTE: N! was included with Qtrans. This is because it's the translational motion that causes the
positions of identical particles to be interchanged, requiring the factor of N! The internal motions
don't interchange particles.

Classically

Qcl = Qtrans,cl Qint,cl

q Ntrans,cl [∫ e − ε trans /kT dpdq] N

Q trans,cl = =
N! N!h 3 N

Q int,cl = q Nint = ∫ dp 3N dq 3N e − εint /kT h 3N

 

CONTRIBUTION OF INTERNAL DEGREES OF FREEDOM TO MACROSCOPIC

PROPERTIES

⎛ ∂ ln Q ⎞ ⎛ ∂ ln Q transQ int ⎞
E = kT2 ⎜ = kT2 ⎜ ⎟⎠
⎝ ∂T ⎟⎠ N,V ⎝ ∂T N,V

⎛ ∂ ln Q trans ⎞ ⎛ ∂ ln Q int ⎞
E = kT2 ⎜ + kT2 ⎜
⎝ ∂T ⎠ N,V
⎟ ⎝ ∂T ⎟⎠ N,V
E= E trans E int
(will equipartition be applicable here?)

A = −kTln Q = −kTln Q transQ int

= −kTln Q trans + −kTln Q int
= A trans + Aint

Likewise: S = Strans + Sint

⎛ ∂ln Q ⎞
But for pressure: p = kT ⎜ ⎟ = p trans + p int = p trans
⎝ ∂V ⎠
N,T
because no V dependence for internal coordinates

Could use the Classical Mechanical approach to compute any average quantity, e.g.

∫  ∫ dq 3dp 3x q 3 , p 3 e (
  )
( )
−ε q 3 , p 3 kT

x=    −ε  q 3 ,p 3 kT
∫  ∫ dq 3dp 3e (   )
 

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5.62 Spring 2008 Lecture #10, Page 6

The factors of h–3 in numerator and denominator cancel.

The Classical picture will prove extremely useful when there are inter-particle interactions.

Non-Lecture
Example of a classical mechanical calculation: particle bound in a deep well near a solid
surface.

ε
β
L

V(z)

0
0 α

0≤z≤α pz = [2mε]1/2 εz = p 2z 2m
α≤z≤L pz = [2m(ε−β)]1/2 εz = p 2z 2m + β

To compute qCl we need

L ∞ ∞ α ∞ L
∫ dz ∫ dp z e − ε(z,pz ) kT = ∫ dp z ∫ dze − pz + ∫ dp z ∫ dze − pz
2 2
qz = 2mkT 2mkT
0 −∞ −∞ 0 −∞ α

= [ α + (L − α)e ] ∫ dp e
∞
−β kT − p 2z 2mkT
z
−∞

= [ α + (L − α)e −β kT
][ 2πmkT] 1/2

1/2

q z = [ α + (L − α)e −β kT
] ⎡⎢⎣ 2πmkT ⎤
h 2 ⎥⎦

The multiplicative contributions from the x and y directions do not have the pre-factor

3/2

q Cl = [ α + (L − α)e −β kT
] ⎡⎢⎣ 2πmkT
h 2
⎤
⎥
⎦
L2
3/2
⎡ 2πmkT ⎤
for kT  β q Cl = ⎢ L3
⎣ h 2 ⎥⎦
3/2
⎡ 2πmkT ⎤
for kT  β q Cl = ⎢ L2α
⎣ h 2 ⎥⎦

revised 2/29/08 8:52 AM

5.62 Spring 2008 Lecture #10, Page 7

Of course this derivation is not quantitatively correct because it is necessary to assume that kT 
β. It is also incorrect because the exact quantum mechanical energy level in the deep, near-
surface well is not at the bottom of the well. But this calculation reveals the qualitative change
in qtrans between the low-T limit (all molecules are adsorbed, thus confined to a volume L2α) and
the high-T limit (all molecules are desorbed).

revised 2/29/08 8:52 AM