CHEN E4330 Supplementary Notes on ACT, Degrees of Freedom, and Partition Functions

I. Partition functions
Definition: a partition function is a number describing the number of energy states available to
a system at a given Temperature.
Note on notation used in Houston: Houston Chapter 3 uses the symbol q and the z
interchangeably when referring to the partition function. It seems that q is usually used when
referring to a total partition function for a given species, while z is usually used to describe
sub-components of the partition function (e.g. the translational, rotational or vibrational
factors). However, the author is not consistent in this regards. In this note packet, I will stick
with using q in all cases, so do not be confused when you see zs in Chapter 3 of Houston.
The mathematical definition for a partition function (see Chapters 19, 20, of Atkins and de
Paula Physical Chemistry book) is:

(1.)
where
n
is the energy contained by energy state n. The net energy can be expressed as a sum
of contributions from different energy modes, or states:

(2.)
where T, R, V, and E stand for translational, rotational, vibrational, and electronic. We can use
this equation, assuming independent degrees of freedom for different energy modes, to
express the total molecular partition function. This is done by inserting equation (2.) into
equation (1.), which we can factorize to obtain equation (3.):

(3.)
where =1/(k
b
T). Since the sum of the product of exponentials can be written as the product of
sums, we can express the total partition function in terms of individual contributions from
different modes. (see page 104 of Houston)
[

][

][

][

(4.)

II. Developing the ACT rate expression
In class on 9-29-14, we were looking at the following bimolecular reaction between A and B,
proceeding through the activated complex AB :
A + B AB products
where we assume a pseudo or quasi equilibrium between the reactants and the activated
complex (AC). The equilibrium reaction is governed by rate constants k
1
and k
-1
, while the
irreversible decomposition of AB into the products is the rate determining step having a rate
constant of k
2
. Under the assumption that k
-1
>> k
1
, k
2
, we used the SSA applied to AB to
derive the following rate expression: (see class notes for full derivation)

(5.)
Because the first reaction is reversible and k
2
is the rate determining step, there is a pseudo
equilibrium between A, B, and AB, meaning we can equate the ratio of k
1
/k
-1
to the
concentration equilibrium ratio (referred to as equilibrium constant in the text) for this
reaction, K
c
=k
1
/k
-1
. Inserting this into (5.) gives:

(6.)
From statistical thermodynamics, we can express K
c
in terms of partition functions (q
i
) for the
activated complex and each of the reactants, as well as an exponential term taking into account
the difference in zero point energy (ZPE) between the reactants and the activated complex.
This difference in ZPEs is the threshold energy, *:

(7.)
Inserting (7.) in to (6.), the rate expression becomes:

(8.)
We now make two more key assumptions for ACT:
1.) The uni-molecular decomposition of AB occurs with a frequency (with units s
-1
)
corresponding to a frequency mode of the complex that is along the reaction pathway. This
means that k
2
=
2.) According to equation (4.), we can write the partition function for AB, q, as a product of the
partition function associated with , q

, multiplied by all other partition function contributions,

which we group together in a single term which we call q: q= q

q . To reiterate, q is a
modified partition function for the activated complex where the term corresponding to the
frequency along the reaction coordinate leading to decomposition has been factored out.
As shown in Houston (pg. 105), the partition function for the vibration along the reaction
coordinate, , can be written as:
q

= (kT/h) (9.)
Using equation (9.) and the two ACT assumptions, the ACT rate expression from equation (8.)
can now be written as:

(10.)
Canceling out the frequency , we arrive at the final expression for the ACT reaction rate:

(11.)

III. Determining the molecular partition function
The overall partition function, q, for a species i depends heavily on the number of atoms
present in species i. N is the number of atoms in species i and determines how many different
translational, rotational, and vibrational energy modes will be present in a molecule because it
is closely linked to the degrees of freedom (DOF) associated with defining the overall potential
of the molecule.
The DOF associated with a molecule is the number of independent parameters needed to fully
define the problem (in our case we seek to define its energetic state). This is given by:
DOF = 3N (11.)
which arises from the fact that we can fully define the energetics a molecule if we know the the
(X,Y,Z) coordinates of each of each of its atoms (ie 3 per atom).
The DOF of a given molecule, and thus the number of vibrational modes for which we need to
calculate a partition function, is determined as follows:
1. Three DOF are used to define the 3-D translational movement of the molecule using the
translational partition function.
2. For molecules with N>=2, the rotational partition function will set 2 DOF in the case of a
linear molecule, and 3 DOF in the case of a non-linear molecule.
3. For molecules with N>=3, we can then say that the remaining DOF for defining the energy
of the system (excluding the internal energy contributions) is set by vibrational energy
modes. For a linear molecule, this means that we will have (3N -5) terms associated with
the vibrational partition function. For a nonlinear molecule, there will be (3N-6) terms
associated with the vibrational partition function.

Table I. Degrees of freedom associated with translational, rotational, and vibrational modes as
a function of the number of atoms in a given molecule (N)
N molecular
orientation
Total
DOF=3N
Degrees of freedom (DOF) Form of the partition
function translational rotational vibrational
1 NA 3 3 0 0 p=p
T
p
E

2 linear 6 3 2 1 p=p
T
p
R
p
V1
p
E

2 non-linear 6 3 3 0 p=p
T
p
R
p
E

3 linear 9 3 2 4 p=p
T
p
R
p
V1
p
V2
p
V3
p
V4
p
E

3 non-linear 9 3 3 3 p=p
T
p
R
p
V1
p
V2
p
V3
p
E

>3 linear 3N 3 2 3N-5 same as above but with
3N-5 p
v
terms
>3 non-linear 3N 3 3 3N-6 same as above but with
3N-6 p
v
terms

****Equations for all partition function types listed in the last column of Table I are given in
Table 3.1 of Houston.
Question: Why didnt we include three (or two) partition function terms for the translational
and rotational terms?
Answer: The equations in Table 3.1 for translational and rotational partition functions have
already taken this into account. For example, the three terms for translation associated with
translation in the X, Y, Z are all identical, giving rise to a 3 in the exponent of p
T
. Similarly, we
see 3 in the exponents of the rotational partition function for nonlinear molecule and 2 for
the rotational partition function of the linear molecule.