Rice-Ramsberger-Kassel-Marcus

Unimolecular Dissociation Theory

McLuckey Summer Lecture Series
Boone Prentice
August 8
th
, 2011
Unimolecular Reactions
Unimolecular reactions are in principal the simplest
type of gas-phase chemical reaction
These reactions are fundamentally important to
understanding the products observed from activated
molecules
Dissociation from a wide variety of activation methods
can be modeled using theories
Collision Induced Dissociation and its analogues
Electron Ionization
Photodissociation
A
E
Products
Activation.Then Reaction
In fact, the reaction step is a second, separate process from
the activation (and competing deactivation) stage
This is why the dissociative rates of many types of
activation methods can be modeled using unimolecular
theories (so long as they obey certain base assumptions)
Types of reactions can include:
Isomerization
Elimination C
2
H
5
Cl C
2
H
4
+ HCl
Dissociation C
2
H
6
2CH
3
A + M A* + M
k
1
k
-1
A* Products
k
2
1)
2)

A Brief History
1880 2000
1889: Arrhenius
concludes that
there is an
energy barrier
to a reaction
and lays
foundation for
concept of
reaction
coordinate
1915: Marcelin
suggests that
activation
energy can be
viewed on a
potential energy
surface
1922: Lindemann
suggests that
unimolecular
reactions consist
of separable
activation and
reaction steps
1926: Hinshelwood
recognizes that the internal
energy and the degrees of
freedom are important in
determining the rate
~1926:
Schrodinger
and
Heisenberg
introduce
quantum
mechanics
1927: Rice, Ramsperger
& 1928: Kassel refine
theory to show that
critical vibrational
oscillators are
responsible for
dissociation and
intramolecular energy
transfer occurs freely,
known as ergodicity
(RRK)
1932: Heisenberg wins
Nobel Prize in physics
1933: Schrodinger wins
Nobel Prize in physics
1935: Evans, Polanyi & 1935:
Eyring develop transition state
theory (TST) to better describe
chemical quasi-equilibrium
involved with a transition state
complex on a potential surface
1952: Rice, Marcus and others merge
TST with RRK, considering individual
vibrational frequencies of the
activated complex
1952: Rosenstock and others
formulate QET
1939: Slater mathematically describes
relation between characteristic bond
frequencies and dissociation
1992: Marcus wins Nobel Prize in
Chemistry (electron transfer)
1956: Hinshelwood wins
Nobel Prize in Chemistry
A First Order Reaction?
Initially, it was unclear as to how analytes were
reacting
If the energy for a reaction was acquired via a collision
then the reaction should not be first order, it should
be second ordercorrect?
1919: Perrin proposed that absorption of thermal
radiation from the vessel walls by molecules led to
reactionbut this intensity would not account for the
observed reaction rates
Lindemann proposed a two step reaction scheme
which is the basis for current theories which
explains this phenomenon
Lindemann Theory
Simplest of the unimolecular reaction theories
First to suggest the unimolecular reactions involved separate
activation and reaction steps
This theory assumes that A* is very reactive and, once formed, it
quickly undergoes deactivation or unimolecular reaction to
products
The conversion of energized analytes into products is slow compared
with the rate of deactivation (k
-1
>>k
2
)
An equilibrium concentration of the energized analytes is quickly
established and is proportional to the unactivated molecules
The rate of reaction, which is proportional to the concentration of
energized molecules, is thereby also proportional to the concentration
of unactivated molecules- making the reaction first order
A + M A* + M
k
1
k
-1
A* Products
k
2
http://en.wikipedia.org/wiki/Ferdinand_von_Lindemann
Lindemann Theory: Rate
Applying the steady-state approximation to
[A*] gives:
Which makes the overall rate:
0 *] [ ] *][ [ ] ][ [
*] [
2 1 1 = = A k M A k M A k
dt
A d
2 1
1
] [
] ][ [
*] [
k M k
M A k
A
+
=

2 1
2 1
2
] [
] ][ [
*] [
k M k
A M k k
A k
+
=

Lindemann Theory: Pressure Limits

Above a certain pressure, k
-1
>>k
2
:
Making the reaction first order w.r.t. the reactant
molecules
Below a certain pressure, k
-1
<k
2
:
Making the reaction pressure dependent, and second
order overall
] [
] [
*] [
1
2 1
2 A k
k
A k k
A k

= =
] ][ [ *] [ 1 2 M A k A k =
Lindemann Shortcomings
The qualitative pressure observations of Lindemanns
Theory hold true experimentally
However, Lindemann Theory rates quantitatively
always fall off at much higher pressures than in
experiments (underestimates the rates) because
collisional activation rate is modeled by simple collision
theory:
This does not take into account internal degrees of
freedom of the molecule which already possess some
rotational and vibrational energy
Does not account for energy level dependence on reaction
rates (in experiments this is observed as non-linearity)
Does not take into account the specificity of the
bond/motion which takes part in the reaction
Hinshelwoods Solution to Simple
Collision Activation
Calculated activation rates could only be made
to agree with experiment if k
1
depended upon
the internal energy of the reactant
The probability of any given reactants level of
activation is given by the Botzmann distribution
By this the quantum states of internal (rotational
and vibrational) motion are taken into account
Modeled internal modes as simple harmonic
oscillators
http://nobelprize.org/nobel_prizes/chemistry/laureates/1956/hinshelwood-bio.html
Hinshelwood Theory: Using the
Boltzmann Distribution
If we start with statistical mechanics, the fraction
of molecules containing a certain energy between
E and E+dE in a single d.o.f. is given by a
Boltzmann distribution:
The total fraction must be 1:
This gives a=1/kT:
dE ae f
kT E/
=
1
0
/
=
}

dE e a
kT E
dE e
kT
f
kT E/
1

=
Hinshelwood Theory: Degrees of
Freedom
If we now consider multiple degrees of freedom (s) and define the
distributed energy such that the amount in degree 1 is between E
1
and E
1
+dE
1
, energy in degree 2 is between E
2
and E
2
+dE
2
, etc.:
Integrating, with the restriction that the sum of the individual
energies must be less than or equal to the total E gives:
Differentiation of this gives the range of energies between E and
E+dE:
s
kT E
s
s
kT E kT E kT E kT E
s
dE dE dE dE e
kT
f
dE dE dE dE e e e e
kT
f
s
...
) (
1
... ...
) (
1
3 2 1
/
3 2 1
/ / / / 3 2 1

=
=
!
... ... ...
1 1 2 1 1
1
...
0 0
3
0
2
0
1 3 2 1
s
E
dE dE dE dE dE dE dE dE
s
E E E
s
E E E E E E
E E
s
s
= =

} } } } } }

s
}}

= =

)! 1 (
)
!
( ...
1
3 2 1
s
dE E
s
E
d dE dE dE dE
s s
s
Hinshelwood Theory: Equilibrium
Proportion
The equilibrium proportion of molecules with total
energy between E and E+dE, distributed any way
between s d.o.f. is, as stated before, the integral over
the range E < E
i
< E+dE:
This fraction can be expressed in terms of the relative
activation and deactivation rates as dk
1
/k
-1
, where dk
1
represents the rate constant for the formation of
molecules having energy between E and E+dE:
dE e
kT kT
E
s
F
kT E s / 1
1
) (
)! 1 (
1

=
dE e
kT kT
E
s k
dk
kT E s / 1
1
1 1
) (
)! 1 (
1


=
Hinshelwood Theory: Activation Rate
In order to get the rate ratio, this must be integrated between the
threshold activation energy for conversion into products and infinity:
Solving this integral under certain conditions gives the approximate
solution:
Strong Collision Approximation: Assuming the energy of the molecule is
completely randomized according to the Boltzmann distribution at every
collision, the activation rate is proportional to the Boltzmann distribution
This differs from the simple collision theory by a factor which takes into
account the number of involved harmonic oscillators
}

= =
*
/ 1
1
1 1
) (
)! 1 (
1
] [
*] [
E
kT E s
dE e
kT kT
E
s A
A
k
k
kT E s
e
kT kT
E
s A
A
k
k
/ * 1
1
1 1
)
*
(
)! 1 (
1
] [
*] [


= =
kT E s
e
kT kT
E
s
Z
k
/ * 1
1
1
)
*
(
)! 1 (

=
Hinshelwood
Improvements/Shortcomings
The Hinshelwood model improves upon the Lindemann
model by taking into account the degrees of freedom of the
reactant
In practice, s is somewhat of a fudge factor used to fit
experimental data
This is because in reality not all of the d.o.f. are involved,
typically the total d.o.f. is used (effective oscillators)
However, Hinshelwood has only addressed the problem
associated with the energy of activation (the k
1
process),
there exist two additional problems with the k
2
process
k2 is assumed to be the same for all energized molecules,
regardless of there degree of activation
There is only a dependence of activation on the number of
frequencies, but there is no dependence of dissociation on the
actual specific frequency of the mode of interest
RRK Theory
In light of the shortcomings of Hinshelwood, it was recognized that
a minimum amount of energy must be localized in specific modes
of molecular motion in order for the unimolecular step to take
place
A molecule is viewed as a system of loosely coupled oscillators,
allowing for the flow of energy but the separateness of normal
modes (effectively individual vibrating bonds)
In order to take this into account, it was recognized that there
needed to be a distinction made in the reaction scheme between
an energized molecule (A*) and an activated molecule (A)
A is a molecule which is passing directly into the final state
A* is a molecule which has sufficient energy to become activated
without further added energy, but which must undergo vibrations
before it becomes activated
A + M A* + M
k
1
k
-1
A
Products
k

A* A
k
2
http://photos.aip.org/quickSearch.jsp?qsearch=Rice%2C+Oscar&group=10&Submit=GO
RRK Theory: Degeneracy
We start with the statistical weight of a molecule with s vibrational
d.o.f. with j quanta of vibrational energy
This can be viewed as the number of ways j objects can fit among s
boxes, and each box can have any number of objects
The number of ways to do this (degeneracy) is given by:
If one particular oscillator has m quanta:
Then the probability that the particular oscillator has m quanta and
all s oscillators have j quanta is the ratio of these:
)! 1 ( !
)! 1 (

+
=
s j
s j
w
)! 1 ( )! (
)! 1 (
'

+
=
s m j
s m j
w
)! 1 ( )! (
! )! 1 ( '
+
+
=
s j m j
j s m j
w
w
RRK Theory: Statistical Energy Location
Applying the Stirling approximation (n!=n
n
/e
n
):
Given that j-1 >> s-1:
Since the total number of quanta j is proportional to the total
energy E and m is proportional to the threshold energy for
decomposition E*:
This is the probability of locating in the dissociation mode a
minimum amount of energy E* out of the total energy E
) 1 ( ) (
) 1 (
) 1 ( ) (
) 1 ( '
+
+
+
+
=
s j m j
j s m j
s j m j
j s m j
w
w
1
) (
'

=
s
j
m j
w
w
1
)
*
(
'

=
s
E
E E
w
w
RRK Theory: Rate Equation
Since energy randomization occurs rapidly, the energy is distributed
statistically and the rate at which the required energy E* passes into
this critical oscillator is proportional to this ratio:
Applying the steady-state approximation again and assuming that
an activated molecule only proceeds to decomposition allows us to
define the rate constant:
k
2
increases with E, because the probability of localizing a given
amount of energy E
0
in one particular mode increases
k
2
decreases as s increases because there are more modes to spread
the energy across (in contrast to the behavior of the rate constant for
activation k
1
)
1
)
*
(
'
*] [
] [

= =
s
E
E E
w
w
A
A
1
2 )
*
( ) (

=
s
E
E E
k E k
RRK Improvements/Shortcomings
Gave a more accurate picture because the reaction rate
had an internal energy dependence
However, the statistical concept of coupled oscillators
is vague and not clearly identifiable with normal modes
(which is why the # effective oscillators # d.o.f.)
RRK also attempts to incorporate the magnitude of the
specific frequency of the critical oscillator
k is the first-order frequency factor for the reaction
For certain molecules this is on the order of average
vibrational frequencies (~10
13
s
-1
), meaning a complete
redistribution of energy on every vibration
However, other reactions have frequency factors higher by
several orders of magnitude.which is unexplained by this
theory
RRKM Theory
RRKM merges transition state theory (TST) with RRK theory
T.S. assumption: Any trajectory along the potential energy
surface which passes through the transition state in the
forward direction will proceed to products without recrossing
via reversal
When combined with the ergodic approximation this means
that the reaction rate coefficient can be calculated from the
rate of trajectories which cross the barrier by the total number
of states in ensemble at the required energy (phase space)
The individual vibrational frequencies of the energized
molecule are considered explicitly
Dependent upon how the various normal mode vibrations and
rotations contribute to reaction
Makes allowance for zero point energies
http://nobelprize.org/nobel_prizes/chemistry/laureates/1992/marcus-autobio.html
RRKM: Basic Assumptions
The time required for dissociation is long relative to the time
required for ion formation/excitation/activation
The time required for dissociation is long relative to the time
required for redistribution of energy over all internal modes of the
ion (ergodicity, energy can slosh around) and the distribution of
reactants is defined by a microcanonical ensemble
Meaning that RRKM does not apply to non-ergodic processes such as
ECD/ETD
The reaction is adiabatic; it takes place on a single potential energy
surface, upon which the motion is classical, that links reactants to
products and is separable from the other molecular motions
The products observed are from competing and consecutive
reactions
There is a unique dividing surface (T.S.) which divides the reactants
from the products which is a point of no return
RRKM Simple Derivation: Case 1
Consider a simple diatomic molecule (e.g. H
2
), with
E=E
o
If we represent the molecule as an oscillator of
frequency , its vibrational states are spaced by:
Only one state is contained in the interval, since there
are no other states available, the rate constant is
simply equal to the bond dissociation rate (vibrational
frequency)
The vibrational frequency is typically viewed as an
upper limit to the reaction rate (independent of E)
H H
v o h E =
h
E o
v =
v
o
= =
h
E
E k ) (
RRKM Simple Derivation: Case 2
Consider a polyatomic molecule, with E=E
o
In the polyatomic, there are more states in the
activated complex at E
o
, so the E/h term needs to
be modified
Modified by the ratio of the number of states in the
transition state [W

(E-E
o
), only 1 in this case] divided
by the total number of states in the activated
complex [W

(E)]
The density of states in the activated complex is
simply the derivative of the number of states,
W(E) = (E) E, which can be substituted in:
H
H
H
H
C
) (
1
) (
1
) (
E h E E h
E
E k
o
o
= =
) (
1
) (
E W h
E
E k
o
=
RRKM Simple Derivation: Case 3
Consider a polyatomic molecule, with E>E
o
Now, more states of the transition complex
are available and since each state is equally
probable, the overall rate constant is the
product of the single state rate constant
and the number of states:
Additionally, reaction path degeneracy
needs to be accounted for:
H
H
H
H
C
) (
) E - (E
) E - (E
) (
1
) (
o
o
E h
W
W
E h
E k

= =
) (
) E - (E
) (
o
E h
W
E k

o
=
RRKM Equation
: reaction path degeneracy
(number of ways to proceed
to the same product)
h: Planks constant
W

(E-E
o
): sum (number) of
states at the transition state
with energy between 0 and
E- E
o
(E): density of states at
energy E back at the reactant
(ways not to fragment)
E
o
: critical energy for reaction
E: total energy
) (
) (
) (

E h
E E W
e k
o

o
=
A* A Products
Reaction Coordinate
E
n
e
r
g
y
E
()
E
o
E
(W)
Transition State Implications
The relative tightness of the
transition state has effects on
the rate of reaction
As internal energy increases, the
number of states grows more
quickly for loose transition states
than for tight transition states
Remember, the number of
transition states is in the
numerator, so more states
means a faster rate
As before with RRK, as the
number d.o.f. increases the rate
decreases because there are
more modes to spread the
energy across
Internal Energy
R
a
t
e
,

l
o
g
(
k
)
looser
tighter
Internal Energy
R
a
t
e
,

l
o
g
(
k
)
smaller # d.o.f.
larger # d.o.f.
Reaction Types
The fragments that are
observed are competing and
consecutive reactions at a
given E
Higher critical energy pathways
have slower rates and, most
likely, wont be observed
Often, rearrangements are low
critical energy, high entropy
processes and can be observed
under certain instrument
conditions
Increasing the internal energy
causes the simple cleavage to
become competitively favored
over the rearrangement
Internal Energy
R
a
t
e
,

l
o
g
(
k
)
simple
cleavage
rearrangement
Internal Energy
R
a
t
e
,

l
o
g
(
k
)
lower critical
energy
higher critical
energy
Metastable Ions
The appearance of metastable ions is governed by the
instrument time scale and the slope of the rate curve
A slower rate curve would give a wider range of energies over
which metastables can appear
Internal Energy
R
a
t
e
,

l
o
g
(
k
)
Abundance
F
+
A
+
m*
F
+
A
+
m*
5.5
4.5
30 s
3 s
Types of Energy Shifts
Kinetic Shift
More energy than the critical energy for fragmentation is required to observe
the pathway
This is needed in order to drive the reaction at a higher rate so that it is fast
enough to be observed on the instrument time scale (Appearance Potential
Ionization Potential in EI)
Increases with d.o.f., E
o
, and the tightness of the transition state
(rearrangements)
Thermal Shift
Less energy than the critical energy for fragmentation is required to observe
the pathway
This is because the molecule already has some internal energy
Tends to counteract kinetic shift
Competitive Shift
More energy than the critical energy for fragmentation is required to observe
the pathway
This can occur in the presence of a competing pathway
More energy is needed drive the desired pathway at a more competitive rate
E
J

: energy of rotational modes which does not contribute to

reaction (adiabatic)
E*: Active energy for in complex
E

: True active energy corrected for zero-point energy

Ea: Energy required to energize molecule
Actual Energy Diagram
In truth, the type of energy is
important and as such the
energy diagram is a bit more
complicated
Additionally, rotational energy
is usually not or only partially
involved with the reaction as
compared with translational
Zero-point energy levels are
accounted for and can vary
between reactants and
activated molecules
Kinetic Isotope Effect
The zero-point energy level is
mass dependent
The critical energy, E
o
, is lower
for lighter masses (e.g. E
o
(H
loss) < E
o
(D loss)
As such, k
H
> k
D
A* A Products
Total
Energy
Energy of
Active Modes
Zero-Point
Level
Classical
Ground State
Total
Energy
Classical
Ground State
E
J
E
j

= E
t

+ E
n

E
o

E
a
E
E
o
Energy of
Active Modes
Zero-Point
Level
E*
E
t

: translational energy along reaction

coordinate
E
n

: energy of active vibrations and

rotations
Calculating a Mass Spectrum (QET)
Due to poor interdisciplinary communication the same RRKM
model was rediscovered by Rosenstock in mass spectrometry and
named quasi-equilibrium theory
1. Identify the relevant fragmentation pathways and the kinetic
scheme
Write the unimolecular rate expressions for all reactions
Calculate the vibrational frequencies and number of states of the
reactant and transition state
Direct Counting
Witten-Rabinovitch approximation
Determine the degeneracy for each reaction path
Determine the relevant critical energies
2. Calculate the rate constants and generate k vs. E curves
3. Integrate the k vs. E curve over the determined reaction time to
generate a breakdown curve
4. Determine the potential energy distribution of formed ions and
convolute this with the breakdown curve to generate the
calculated mass spectrum
Fragmentation Pathways
Generate a theoretical mass spectrum of
trimethylurea using RRK theory
A
B
F
G
D
C
M
k3
k2
k1
k4
k5
k6
Rate Expressions: k vs. E Curve
Write simple rate expressions for each
pathway
Using NIST and literature data for reported
critical energies
Using IR frequency stretches for estimated
frequency factors
Breakdown Curve
Estimate the time for ionization of the molecule and its departure from
the source
Generate a breakdown curve of ion concentration over the relevant range
of energies
Estimated Internal E Distribution
Estimated internal energy
distribution given by 70eV EI
Convolute this with the
breakdown curve
Theoretical Mass Spectrum
Theoretical vs. Actual Spectrum
http://webbook.nist.go
v/cgi/cbook.cgi?ID=C63
2144&Units=SI&Mask=
200#Mass-Spec
References
Baer, T., Mayer, P.M. Statistical Rice-Ramsperger-Kassel-Marcus
QuasiequilibriumTheory Calculations in Mass Spectrometry. Journal of
the American Society for Mass Spectrometry 8, 103-115 (1997).
Cooks, R.G., Beynon, J.H., Caprioli, R.M., Lester, G.R. Metastable Ions,
Elsevier Scientific, 1973.
Forst, W. Theory of Unimolecular Reactions, Academic Press, 1973.
Futrell, J.H. Gaseous Ion Chemistry and Mass Spectrometry, Wiley & Sons,
1986.
Gilbert, R.G., Smith, S.C. Theory of Unimolecular and Recombination
Reactions, Blackwell Scientific Publications, 1990.
Green, N.J.B. Comprehensive Chemical Kinetics, Volume 39- Unimolecular
Kinetics Part 1: The Reaction Step, Elsevier, 2003.
Laidler, K.J. Theories of Chemical Reaction Rates, McGraw-Hill, 1969.
McQuarrie, D.A., Simon, J.D. Physical Chemistry: A Molecular Approach,
University Science Books, 1997.
Notes from Graham Cooks 624 Class
Notes from Scott McLuckeys 624 Class