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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 x average kinetic energy in x-direction

x =

x P ( x ) d x
1/2 1/2 x
kT
x e

P ( x ) = ( kT) 1 x = kT 1 x = kT
1/2

1/2 kT x
e x d x

1/2

kT ( kT)1/2 = 1
kT 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

x1/2 e ax dx =

1/2 2a 3/2
1/2

( dimension: ( dimension:

length 3/2 length1/2

) )

x 1/2 e ax dx = ( a )

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. = +

x y

z
1
2kT

+ 2kT + 2kT = 2kT

1

Each degree of freedom contributes 2kT to total energy. Agrees with result from ensemble average

5.62 Spring 2008 3 ln Q trans = E = kT2 = P E = kT

N,V 2 T
CLASSICAL MECHANICAL DESCRIPTION calculate

Lecture #10, Page 2

State of a molecule is described by p momentum, q position. The energy of ~ ~ Nmolecule system is (p 3N, q 3N), which is a continuous function of 6N variables. ~ ~

q trans = e i
i

kT

let's assume this by analogy

( p,q )/kT
~ ~

dp dq
~ ~

quantum

classical integral over 3 momentum and 3 position coordinates for each particle

q trans,cl = =V

dq x dq y dq z dp x dp y dp z ep
2

= p x + p y + p z
2

/ (2mkT)
2

dp x ep x /2mkT

dp y e

p 2 /2mkT y

dp z ep z /2mkT

2 3/2 3 = V dp x e p x /2mkT = V (2mkT)

[qtrans,cl. should be dimensionless, but this has units m3l6t3 = 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 + t. If the system returns to q(t1), p(t1) at t2, then it must move to q(t1 + t), p(t1 + t) at t2 + t.] 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.
2mkT V , we see that we need a factor of h3 in the denominator Comparing to q trans,qm = h2 of qtrans,cl.. In fact, it turns out that to construct a partition function from a classical Hamiltonian, this h3 factor is required, so our assumption above must be corrected:
3/2

q trans,cl = Q trans,cl

1 e classical 3 h

kT

dp dq
~ ~ kT

(dimensionless)
N N = V 2mkT dp dq N! h 2 3N/2

qN 1 = trans,cl = e classical 3N N! N!h

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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 mol1 at 300K

= 10 20 kcal mol1 (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 1019 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.
(p 3N ,q 3N ) kT
~ ~

P () =

g()e

Classical Boltzmann distribution function

(p

3N

,q 3N ) kT
~

d p 3N d q 3N N!h 3N
~ ~

g() is the density of states, often denoted as (). It has units (energy)1. 1 1 1 3 = P ( ) d = x + y + z = 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
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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 = trans + int
internal quantum #'s

quantum #'s N,M,L

where int = energy from internal degrees of freedom

q = ei
i

kT

+ = e ( trans int )

kT

all molecular states

all molecular states

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

q = ( e trans
translational states
kT

)( e

int

kT

internal states

q=

qtrans

qint

( q transq int )N Q=
N! Q = QtransQint

INTERNAL MOLECULAR PARTITION FUNCTION N q = trans q N N! int CANONICAL PARTITION FUNCTION CANONICAL TRANSLATIONAL PARTITION FUNCTION CANONICAL INTERNAL PARTITION FUNCTION

Q trans =

QN trans N!

Q int = Q N int

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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 trans,cl =

qN trans,cl N!

[ e trans /kT dpdq] N = N!h 3 N

Q int,cl = q N = dp 3N dq 3N e int /kT h 3N int

CONTRIBUTION OF INTERNAL DEGREES OF FREEDOM TO MACROSCOPIC PROPERTIES
ln Q E = kT2 = T N,V ln Q trans E = kT2 T N,V E= E trans
(will equipartition be applicable here?)

ln Q transQ int kT2 N,V T + ln Q int kT2 T N,V E int

A = kTln Q = kTln Q transQ int = kTln Q trans + kTln Q int = A trans + Aint
Likewise: S = Strans + Sint

ln Q p = kT = p trans + p int = p trans V

N,T because no V dependence for internal coordinates
But for pressure: Could use the Classical Mechanical approach to compute any average quantity, e.g.
q 3 , p 3 dq 3dp 3x q 3 , p 3 e (
) x= q 3 ,p 3 kT dq 3dp 3e ( )

kT

revised 2/29/08 8:52 AM

5.62 Spring 2008 The factors of h3 in numerator and denominator cancel.

Lecture #10, Page 6

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. L V(z)

0 0 0z zL To compute qCl we need

pz = [2m]1/2 pz = [2m()]1/2 z = p 2 2m z 2 z = p z 2m +

qz =

= [ + (L )e = [ + (L )e
0

dz dp z e (z,pz ) kT =
kT kT

dp z dze pz
0

2mkT

+ dp z dze pz

2mkT

] dp e ][ 2mkT]
z

p 2 2mkT z 1/2
1/2

q z = [ + (L )e

kT

] 2mkT h2

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

q Cl = [ + (L )e for kT for kT

kT

] 2mkT h2
3/2

3/2

L2

2mkT q Cl = h2 2mkT q Cl = h2

L3
3/2

L2

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5.62 Spring 2008

Lecture #10, Page 7

Of course this derivation is not quantitatively correct because it is necessary to assume that kT . It is also incorrect because the exact quantum mechanical energy level in the deep, nearsurface 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 L2) and the high-T limit (all molecules are desorbed).

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