IC T Reaction Rate Theory

k
+
A B AB

+ E

reaction coordinate
IC-1/44 Lecture-3 02-10-2003
IC T The Arrhenius Equation
k
+
A B AB

d [AB]
r = = k [A] [B]
dt

- Eact / RT
k = ve
E
Svante
+ Eact Arrhenius
1859 - 1927
Nobel Prize 1903

Empirical !
reaction parameter IC-2/44 Lecture-3 02-10-2003
IC T Transition State Theory

To determine the rate we must know the concentration on top

of the barrier.

The relative concentration between a reactant and product in a

Chemical reaction is given by the Chemical Equilibrium

The Chemical Equilibrium is given by the chemical potential

of the reactant and the product. That we know how to calculate.
k

 A A  B B C C   D D

k

dG
d
  A  A   B  B  C C   D  D   
i
i i  0

IC-3/44 Lecture-3 02-10-2003

IC T The Chemical Equilibrium

The chemical potential for the reactant and the product can be
determined if we know their Partition Functions Q.
 qiNi 
  ln ( )
  ln (Qi ) 
   kT 
Ni!  qi
i   kT     kT ln ( )
 N i  
N i

Ni
 
Here Qi is the partition function for the gas i and qi the
partition function for the gas molecule i
Let us assume that we know qi then
i C D  A  B
 qi   qC   qD   qA   qB 
i  N   1         
 i  NC   ND   NA   NB 

IC-4/44 Lecture-3 02-10-2003

IC T The Chemical Equilibrium
piV
If we assume an ideal gas Ni 
kT
and normalize the pressure with p0=1 bar
C D C D
 qC   q D   pC   p D 
    C  D  A  B    
V  V   kT   p0   p 0 
K (T )  A B
   A B
 q A   qB   p0   p A   pB 
       
V  V   p0   p0 
We obtain the important result that the Equilibrium Constant K(T)
is given by the Partitions Functions of the reactants and products
Thus we can determine the concentration of a product on top of the
barrier if we know the relevant Partion Functions
IC-5/44 Lecture-3 02-10-2003
IC T Partition Functions
Obviously are Partition Functions relevant. We shall here deal
with the Canonical Partition Function in which N, V, and T are
fixed.
Remember, that although we talk of a partition function for an
individual molecule we always should keep in mind that this only
applicable for a large ensample of molecules, i.e. statistics
Consider a system with i energy levels with energy ei and
degeneration gi  i / k B T
e

Pi 
q   gi e
i 0
 i / k B T

e

 i / k B T

i 0

Where Pi is the probability for finding the system in state i

IC-6/44 Lecture-3 02-10-2003
IC T Ludwig Boltzmann
(1844-1906)

N!
S tot  k B ln(W ) W 
 Ni! i
  i / RT
e
Pi  

 e
  i / RT

i0
Boltzmann Statistics:
The high temperature/diluted limit of S = k ln (W)
Real statistical thermodynamics
There is some really interesting Physics here!! IC-7/44 Lecture-3 02-10-2003
IC T Partition Functions
Why does the partition function look like this?
Lets see if we can rationalize the expression:
Let us consider a system of N particles, which can be distributed
on i states with each the energy ei and Ni particles. It is assumed
the system is very dilute. I.e. many more available states than particles.
Ni Ni
Pi  ;  N i  N ;  Pi    1 Constraint 1
N i i i N

Etot
Etot    i N i ;  Pi i    Constraint 2
i i N

Requirement: The Entropy should be maximized (Ludwig Boltzmann)

IC-8/44 Lecture-3 02-10-2003

IC T Partition Functions
S tot
S 
N
  kB i
Pi ln ( Pi ) Where we have utilized
Stirling approximation:
ln ( N !)  N ln ( N )  N Only valid for huge N
Problem: Optimize the entropy and fulfill the two constraints at the
same time. USE LAGRANGE UNDERTERMINED MULTIPLIERS
_
f ( Pi )  S  S ( Pi )  1 (  Pi  1)  2 (  i Pi   )
i i

0 0
 
  S ( Pi )  1  Pi  2   i Pi 
f ( Pi )
  i i  0
Pi Pi
IC-9/44 Lecture-3 02-10-2003
IC T Partition Functions
Result: The Entropy Maximized when
  2
  1 1   i
 kB 
Pi  e e kB

Ni Ni
If we now utilize the first constraints: Pi 
N
;  Ni  N ;
i
 Pi  
i i N
1

  2   2
  1  1   i   1  1   i
P i
i  1  ei
 kB 
e kB
 e  kB 
e
i
kB

 1  2
 1   i
e  kB 
 e kB
Which reminds us of q the partition function
i
IC-10/44 Lecture-3 02-10-2003
IC T Partition Functions
Etot
The second constraint: Etot    i N i ;  Pi i   
i i N
We have to relate the average energy to some thermodynamical data
k BT
 Particle in a box
2 i=1, h2/8mL2

Now if we wants to perform the

sum above we need to have an 2
i=2, h /8mL
2

analytical expression for the Amplitude

energy in state i 0
2 2
i=3, h /8mL

This can be found by isin(ix/L)

considering
0 L
a particle confined in a box Lenght of box
IC-11/44 Lecture-3 02-10-2003
IC T Partition Functions
Particle in a box
ˆ  2 2
H  , Hˆ i   i i 2
i=1, h /8mL
2

2m
2 2
2 2 i=2, h /8mL
i h
i   i 2
c

Amplitude
2
8ml H 2 2
H ĤĤ 0
2m
2 2
i=3, h /8mL

By inserting this in the

isin(ix/L)
result of constraint 1 and
assuming close lying states 0 Lenght of box L

 1     2 ci 2
 1   2 i  1 k B 2k B ml 2
qe  kB 
 e kB
 e
kB
di  
i 0
2 2c h 22
IC-12/44 Lecture-3 02-10-2003
IC T Partition Functions
Utilizing this in constraint 2
  2 i  2 ci 2
 1k B 2k B ml 2
 e  i ce
2 kB
kB
di
k BT i
2 2 h 2 2 1k B
   Pi i  i
 0
 
2 i q 2k B ml 2
2k B ml 2 22
h 2 2 h 2 2

1
Thus 2  I.e. temperature is just a Lagrange multiplyer
T

IC-13/44 Lecture-3 02-10-2003

IC T Partition Functions
 1  2
 1   i
Since constraint 1 gave e  kB 
 e kB

Since constraint 2 gave 1

2 
T
  2
  1 1   i
and the entropy is max for  kB 
Pi  e e kB

i i
 
e k BT
e k BT Thus the form of the partition
Pi  
 function comes as a result of
 i q maximizing the entropy with
e
i
k BT
2 constraints
IC-14/44 Lecture-3 02-10-2003
IC T Translational Partition Functions

As we have assumed the system to be a particle capable of moving

in one dimension we have determined the one-dimensional
partition function for translational motion in a box of length l

l 2 k B mT
qtrans 
h

Now what happens when we have several degrees of freedom?

If the different degrees of freedom are independent the Hamiltonian

can be written as a sum of Hamiltonians for each degree of freedom
Htot=H1+H2+….

Discuss the validity of this: When does this not work? Give examples
IC-15/44 Lecture-3 02-10-2003
IC T Translational Partition Functions

If the hamiltonian can be written as a sum the different coordinates

are indrependant and
H E j ( H a  H b  H c )

q  e k BT
 e k BT
 e k BT

j j ikl

 (  i a  k b  l c )  i  k   l

 e k BT
 e k BT
e e k BT k BT
 qa qb qc
ikl i k l

Thus for translational motion in 3. Dimensions.

( 2 m k BT ) 3 / 2
qtrans = qtrans qtrans qtrans =
3D x y z 3D
q
trans  V
h3
IC-16/44 Lecture-3 02-10-2003
IC T Partition Functions
It is now possible to understand we the Maxwell-Boltzman
distribution comes from
 i  i
  k BT  k BT
e e
 Pi  1 
i
 f ( p x ) dp x   q
di   l 2 k B mT
di
 0 0

h
 i2 p2  p x2
  2 m k BT  2 m k BT
e e
 f (p

x ) dp x  
0 2 k B mT
2 p di  
 2 k B mT
dp x

 p x2 f ( px , p y , pz )  f ( px ) f ( p y ) f ( pz )
2 mk BT
e
f ( p x )dp x  dp x  m 
3/ 2
 mv 2 / 2 k BT
2 mk BT f (v)  4   2
v e
 2 k B T 
IC-17/44 Lecture-3 02-10-2003
IC T Maxwell-Boltzmann
distribution of velocities
3/ 2
 m   mv 2 / 2 k BT
f (v)  4   2
v e
 2 k B T 

Average:
1/ 2 1/ 2
 8k BT   8k BT 
v    ; u   
 m    
500 – 1500 m/s at 300 K IC-18/44 Lecture-3 02-10-2003
IC T Partition Functions
Similarly can we separate the internal motions of a molecule in
Part involving vibrations, rotation and nuclei motion, and
electronic motion i.e. for a molecule we have
q  qtrans qrot qvib qelec qnucl
Now we create a system of many molecules N that are in principle
independent and as they are indistinguishable we get an overall
partition function Q

qN
Q 
N!
What if they were distinguishable ???
IC-19/44 Lecture-3 02-10-2003
IC T Partition Functions
What was the advantage of having the Partition Function?
  ln(Q)  
   k BT   S   k BT ln (Q) NV 
 N V ,T T
  ln(Q)    ln(Q) 
E  k BT 2   p  k BT  
 T  N ,V  V  N ,T

qN
Q 
N!
C D C D
 qC   q D   pC   p D 
    C  D  A  B    
V  V   kT   p0   p0 
K (T )  A B
   A B
 q A   qB   p0   p A   pB 
       
V  V   p0   p 0 
IC-20/44 Lecture-3 02-10-2003
IC T Partition Functions
Similarly can we separate the internal motions of a molecule in
Part involving vibrations, rotation and nuclei motion, and
electronic motion i.e. for a mulecule we have
q  qtrans qrot qvib qelec qnucl
Now we create a system of many molecules N that are in principle
independent and as they are indistinguishable we get an overall
partition function Q

qN
Q 
N!

IC-21/44 Lecture-3 02-10-2003

IC T The Vibrational Partition Function
Consider a harmonic potential  i  (i  12 ) h
 i  i h   i  12 h
'

  12 h / k B T
e
qvib   e
 ( i  12 ) h / k B T

i 0 1  e  h / k B T

1
q'
 e i h / k B T

1  e  h / k B T
vib
i 0

k BT
q'
vib,class for h  k BT
h
If there are several normal modes:  12 h i / k B T
e
qvib   i 1 e  h i / k B T

IC-22/44 Lecture-3 02-10-2003

IC T The Rotational (Nuclear) Partition Function

1 1 1
j ( j  1) h 2
I  r 2  
j   m1 m2
8 2 I
j ( j 1) h 2
 
1
qrot 

 (2 j  1)
j 0
e 8 2 I k BT

 j ( j 1) h 2

1
 d ( j( j  1)) e
8 2 I k BT

 0

1 8 2 I k BT h2
 for T 
 h2 8 2 I k B
Notice: Is not valid for H2 WHY? TRH2=85K, TRCO=3K
IC-23/44 Lecture-3 02-10-2003
IC T The Rotational (Nuclear) Partition Function
Molecular  Types of molecules
symmetry
The Symmetri factor:
This has strong impact C1, Ci, and 1 CO, CHFClBr, meso-
on the rotational energy Cs tartraric acid, and CH3OH
levels. Results in fx
C2, C2v, and 2 H2, H2O2, H2O, and trans-
Ortho- and para-hydrogen C2h dichloroethylene

C3v and C3h 3 NH3, and planar B(OH)3

For a non-linear molecule:

3/ 2
1  8 k BT
2

qrot     I A I B IC
  h 2

IC-24/44 Lecture-3 02-10-2003
IC T Effect of bosons and fermions

If two fermions (half intergral spin) are interchanges the total wave
function must be anti symmetric i.e. change sign.
Consider Hydrogen each nuclei spin is I=1/2
From two spin particles we can form 2 nuclear wave function:
 nuclear
symmetric
and  nuclear
Antisymmetric
which are (I+1)(2I+1)=3 and I(I+1)=1
degenerate respectively

Since the rotation wave function has the symmetry  Rot J

 (1) J
is it easily seen that if the nuclear function is even must j be odd and
visa versa j ( j 1) h 2 j ( j 1) h 2
   
qrot ,nucl  I (2 I  1)  (2 J  1)e 8 2 I k BT
 ( I  1)(2 I  1)  (2 J  1)e 8 2 I k BT

J even J odd
2
j ( j 1) h j ( j 1) h2
   
qrot ,nucl   (2 J  1)e
J even
8 2 I k BT
3  (2 J  1)e
J odd
8 2 I kB T

IC-25/44 Lecture-3 02-10-2003

IC T Ortho and Para Hydrogen
This means that our hydrogen comes in two forms: Ortho Hydrogen
Which has odd J and Para Hydrogen which has even J incl. 0
Notice there is 3 times as much Ortho than Para, but Para has the
lowest energy a low temperature.
If liquid Hydrogen should ever be a fuel we shall see advertisements
Hydroprod Inc.

Absolute Ortho free Hydrogen for longer mileages

IC-26/44 Lecture-3 02-10-2003

IC T Liquid Hydrogen

This has severe consequences for manufacturing Liq H2 !!

The ortho-para exchange is slow but will eventually happen so if we

have made liq. hydrogen without this exchange being in equilibrium
we have build a heating source into our liq. H2 as ¾ of the H2 will
End in J=1 instead of 0.

j ( j  1) h 2 h2
 j 1  2  2  85  k B  170  R  1, 4kJ
8 I2
8 I
2

3
T 252,87 C
H H 2 vap  0,9kJ / mol Internal energy   J 1  1, 06kJ / mol
4

i.e. 11% loss due to the internal conversion of Ortho into Para hydrogen
IC-27/44 Lecture-3 02-10-2003
IC T The Electronic Partition Function
0 1
 
qel (T )   e 0 e k BT
  e1 e k BT
 ...
h
 0   D0   De 
2

Potential Energy (arb. units)

2

Does usually not contribute X2 2X

exceptions are NO and fx. H
atoms which will be twice 1

degenerate due to spin

-De -D0
What about He, Ne, Ar etc??
0 h/2

0 2 4 6 8

Distance (arb. units)

IC-28/44 Lecture-3 02-10-2003

IC T Partition Functions Summary
Partition functions of a diatomic molecule
(per degree of freedom)

translation vibration rotation

( 2 m kBT ) 1/ 2 1 8 2 Ik B T
qtrans /l= qvib   h / k B T
qrot 
h 1 e h2
Huge for any usually equals 1 large:
reasonable size of l unless vibrations have H2: 2.9 at 500 K
H2 : 1.8*1010m-1at 500 K very low frequency CO: 180 at 500 K
CO: 6.8*10 m at 500 K
10 -1
H2: 1.000 at 500 K Cl2: 710 at 500 K
Cl2: 1.1*1011m-1 at 500 K CO: 1.002 at 500 K
Cl2: 1.250 at 500 K

IC-29/44 Lecture-3 02-10-2003

IC T Partition Functions Example
Knowing the degrees of internal coordinates and their energy
distribution calculate the amount of molecules dissociated into
atoms a different temperatures.
T(K) KH2(T) pH/p0 KN2(T) pN/p0 KO2(T) pO/p0

298 5.81*10-72 2.41*10-36 6.35*10- 2.52*10-80 6.13*10-81 7.83*10-41

160

1000 5.24*10-18 2.29 *10-9 2.55*10-43 5.05*10-22 4.12*10-19 6.42*10-10

   
2000  3.13*10-6  1.76*10-3 2.23*10-18 1.80*10-9 1.22*10-5 3.49*10-3
   
3000  1.77*10-3  1.72*10-1 1.01*10-9 3.18*10-5 5.04*10-1 5.01*10-1
     
   
We see why we cannot make ammonia in the gas phase but O radicals
may make NO at elevated temperatures
IC-30/44 Lecture-3 02-10-2003
IC T Surface Collisions
surface
Consider a box with volume V
p vx
v x tA  V  dA
k BT
vxt
 
1
rcoll  surf  
tA 0
f (v x )V (v x ) dv x    v x f (v x )dv x
0

 mv x2
p m 
 v
2 k BT
x e dv x
k BT 0
2 k BT
p p k BT p What are
 vx  
k BT k BT 2 m 2 mk BT the
numbers?
IC-31/44 Lecture-3 02-10-2003
IC T Surface Collisions
How many are successful in reacting?50
Simple Maxwell-Boltzman distribution
40


Energy (kJ/mol)
vx > vmin

 uf (u) du
umin
30

T=1000K
vx < vmin

P  
20

E

 uf (u ) du
0
10 T=600K

T=300K
H
0

 3/ 2 Density
   Reaction Coordinate

u 4  2 k BT
2
 u 3 e u / 2 k BT
du

 min
3/ 2

  
0 4  2 k BT
 u 2 / 2 k BT
 3
u e du

 e E / kBT
IC-32/44 Lecture-3 02-10-2003
IC T Transition State Theory
Consider the following reaction: R#
R 
 R #
 P
#
qq`#
d  P 
 
#
q
 R  K R  
# #
R
dt q E

How?
q
P
 is a frequency or trial factor in the
reaction coordinate
R

 R  q
We assume that R and R# are in Equilibrium #
#
  ln(Q)   #
 
 R   R#    k BT 
 N V ,T
 K
R q
IC-33/44 Lecture-3 02-10-2003
IC T Transition State Theory
By splitting the partition function in the transition state

d  P q #
1 q#
  q# R   h
R
dt q  q
1 e k BT

Assuming k B T  h ex  1 x
k BT
q  for h  k BT
h

d  P  k BT q # k BT q #
  R   kTST  R  kTST 
h q
dt h q
IC-34/44 Lecture-3 02-10-2003
IC T Transition State Theory
The partition function q# can conveniently be split further: R#
q`#=q`#vq#0e-E/kT
R 
 R #
 P
#
qq`#

k BT q0#  E / k BT
kTST  e   e  E / k BT
h q E

Which basically is the Arrhenius

q
P
form
If q0# ~ q ~1x1013s-1 R
Relation to Thermodynamics

k BT k BT G0# / RT k BT S0# / R H 0# / RT

kTST  K# kTST  e  e e
h h h
IC-35/44 Lecture-3 02-10-2003
IC T Transition State Theory
Tight TST: Loose TST:
q# << q q# >> q
Think of
R# R# some examples

E Temperature
E E
E dependence of
R R prefactor

P P
reaction coordinate reaction coordinate
9
10 < < 10
13
s
-1
10
13
< < 10
17
s
-1

S# negative S# positive

IC-36/44 Lecture-3 02-10-2003
IC T Transition State Theory on Surfaces

Indirect adsorption of atoms:

An atom adsorbs into a 2-dim mobile state, we have Ng gas atoms,
M sites on the surface, and N# atoms in the transition state
A    A #
mobile
M
N0 
A # mobie  Amobil  A

dN A*
g   #  N #  K # N g  A 
N A
dt M

d A dN A K #Ng K# V
   p A  kTST p A
dt Mdt M M k BT
IC-37/44 Lecture-3 02-10-2003
IC T Transition State Theory on Surfaces
 ln(Q )
Now what is K ?
#
g   #   k B T
N
Ng
q g q#N #
Qgas  ; Q# 
Ng! N #!

qg  q 3D
trans ; q#  q q #

2D
trans

N# q# qtrans
2D
K#   3D
Ng qtrans
IC-38/44 Lecture-3 02-10-2003
IC T Transition State Theory on Surfaces
d A dN A K #Ng K# V
   p A  kTST p A
dt Mdt M M k BT
 K# V q# qtrans
2D
V This corresponds to the
kTST   3D
M k BT M qtrans k BT collision on a surface since
k BT A  2 m k BT  / h 2 V the atoms are still free to

M h V  2 m k BT  3 / 2 / h 3 k BT move in two dimensions
A 1
 
M  2 m k BT  N0  2 m k BT 
d A* M d A* 1 dN A*
d A* pA N0   
 dt A dt A dt
dt N0  2 m k BT  pA
rcoll .surface 
 2 m k BT 
IC-39/44 Lecture-3 02-10-2003
IC T Transition State Theory on Surfaces
Direct adsorption of atoms: M is total number
of sites
M 1
A    A #
immobile N0   2 M´ is number of
A a free sites
A # immobile  Aimmobile 
M !
Q #
 (q# ) N#
N # ! ( M   N # )!
 g  #
N# q# q #
K #
  (M   N# ) K  M (*   # )
#
Ng qg qg
Why?
(*   # )  *  (1   A ) IC-40/44 Lecture-3 02-10-2003
IC T Transition State Theory on Surfaces
K # V  ( M   N # ) q# V
kTST  
M k BT M qg k BT
q# q2#D vib V
  ( *   # ) 3D
qtrans k BT
V * q2#D vib
 3D
h qtrans
2
 k BT  3
  h
V *  h 2 D 
( E  h 2 D  vib )

 e k BT

h V ( 2mk B T ) 3/ 2

2
 k BT  2
  h  ( E  h 2 D  vib )
* h 
 2D 
 e k BT

2mk B T ( 2mk B T )
2
 k BT  2
  h  ( E  h 2 D  vib )
N 0 * h
 2D 
 e k BT

N 0 2mk B T (2mk B T )

 * S 0 (T ) (1   A ) S 0 (T )
 
N 0 2mk B T N 0 2mk B T
IC-41/44 Lecture-3 02-10-2003
IC T Transition State Theory on Surfaces
d A S 0 (T ) p A
 kTST p A  ( 1  A )
dt N 0 2 mk BT
M q2#D vib q2#D vib q2#D vib
S 0 (T )  2D
 2D
 2D
qtrans qtrans qtrans unitcell
M
2D
qtrans A (2 mk BT ) (2 mk BT )
q 2D
trans unitcell    a 2

M M h2 h2
2
 k BT  2 Notice adsorption
  h ( E  h 2 D  vib ) always result in loss of
S 0 (T ) 
q2#D vib
  h 2 D  e

k BT entropy
q 2D
trans unitcell a 2 ( 2mk B T )
There may also be steric
2 h 2 D _ vib
 k BT   hindrance leading to
   e k BT
4.0 *10 3  0.09 reduced S
 h 2 D  IC-42/44 Lecture-3 02-10-2003
IC T Transition State Theory on Surfaces

What happens in the regime between direct and indirect adsorption?

The atoms breaks free of the site and start to diffuse around in
1 2x 2y
V ( x, y )  V0 ( 2  cos( )  cos( ))
2 a a
2 h 2 D  vib
 k BT   a 2 ( 2 mk B T )
Eventually   e k BT

 h 2 D  h2
# 0# E
q q 
S 0 (T )  2D
2 D  vib
 2D
2 D vib
e k BT

q trans unitcell q trans unitcell

2 h ||
E 
"0 # 2 Eact
q  
 2D
2 D  vib
e k BT
 S 00 e k BT

q trans unitcell IC-43/44 Lecture-3 02-10-2003

IC T Transition State Theory on Surfaces
Indirect adsorption of molecules:
d A dN A K #Ng K# V
     pA  kTST p A
dt M dt M M k BT

N q#  VK # V 2D
qtrans #
qrot #
qvib
K #
  kTST   3D gas gas
Ng q gas k BTM M h qtrans qrot qvib
# #
1 qrot qvib

N0 2mk BT qrot
gas gas
qvib

d A pA q #
q #
 kTST p A  S0 (T ) S (T )  rot vib
dt N 0 2mk BT 0
q gas q gas rot vib

Notice that if the precursor is sufficiently loose S0(T)=1.

IC-44/44 Lecture-3 02-10-2003
IC T Transition State Theory on Surfaces
Direct adsorption of molecules:
 g  #
M !
Q #
 # N#
(q )
N # ! ( M   N # )!

#
N# q # q
K #
  (M   N# ) K #
 M (*   # )
Ng qg qg
K # V *V q '#
kTST   3D gas gas
M k BT h qtrans qrot qvib
1
 S0 (T ) (1   A )
N 0 2 mk BT
IC-45/44 Lecture-3 02-10-2003
IC T Transition State Theory on Surfaces
d A pA
 kTST p A  S 0 (T ) (1   )
dt N0 2 mk BT
Mq '# q '#
S 0 (T )  2D gas gas
 2D gas gas
q trans q rot q vib qtrans unitcell q rot q vib

E E
 
q '#  q '# 0 e k BT
 qvib
#0
q #frus
0
 rot q #0
frus trans e
k BT

Reaction
coordinate
CO-vibration Frustrated Frustrated Frustrated Frustrated
Rotation x Rotation y Translation x Translation y
O

C O O O O O

C C C C C

IC-46/44 Lecture-3 02-10-2003

IC T Transition State Theory on Surfaces

Reactions between surface species: A  B   AB  #

 AB # q AB #
AB  #  AB   
K#  
 A B q A qB

d AB #
 kTST A B   AB # K # A B
dt
 AB # k BT q AB
'#

 A B  k  A B
#

h AB # q A qB

'# '0 # E E
A B  AB # A B  AB #
k BT q k BT q  
k  AB #
 AB #
e k BT
 k0 e k BT

h q A qB h q A qB
IC-47/44 Lecture-3 02-10-2003
IC T Transition State Theory on Surfaces
The reverse process:
AB     AB  
#

AB   #
 A  B 

d AB
  k  AB  *


dt

'# '0 # E E
AB  AB # AB  AB #
k BT q k BT q  
k  AB #
 AB #
e k BT
 k0 e k BT

h q AB h q AB

IC-48/44 Lecture-3 02-10-2003

IC T Transition State Theory on Surfaces
Considering both processes and equilibrium:
d AB #
 k  A B  k  AB*  0
dt
#
AB **
E  E A B  AB #
 AB  AB #
k q AB
K eq    e k bT EA+B-AB#
EAB-AB#
k q A qB
A*+B*

H
S H

K eq  e
AB*+*
kB kbT
e
Reaction Coordinate
Notice how the Keq is alone determined
from initial and final state partition functions. IC-49/44 Lecture-3 02-10-2003
IC T Transition State Theory on Surfaces
Desorption:
AB   AB  #

AB #  AB  
N AB# #
q AB  AB# #
q AB
 AB#    AB  K#  
M q AB  AB q AB
d AB  AB# N AB#
  kTST AB   AB# K # AB 
dt M
'#
k BT q AB
  AB
h q AB
Ea
'0 # E 
k BT q AB 
 e k BT
 AB  e k BT
 AB
h q AB
IC-50/44 Lecture-3 02-10-2003
IC T Transition State Theory on Surfaces
E Adsorbed Transition Desorbed Preexponential

d AB  a state state state factor

  e k BT
 AB
dt mobile  1015 s-1
System Prefactor s-1 Ea kJ/mol
CO/Co(0001) 1015 118 immobile  10
13
s
-1

CO/Ni(111) 1015 130

CO/Ni(111) 1017 155
CO/Ni(111) 1015 126
mobile  1014-16 s-1
CO/Ni(100) 1014 130
CO/Cu(100) 1014 67
immobile 13 -1
 10 s
CO/Ru (001) 10 16
160
CO/Rh(111) 1014 134

k BT q 'AB
0#
Ea  E  k B T ;   e
h q AB
How? IC-51/44 Lecture-3 02-10-2003
IC T Transition State Theory on Surfaces

If the details of the transition state can be determined can the rate
over the barrier be calculated.

Details of the transition state are difficult to access:

•Low concentration
•Short lifetime.

Often determined by ``First Principle´´ calculations, but are only

accurate to say 0.1 eV or 10 kJ/mol.

IC-52/44 Lecture-3 02-10-2003