Research: Science and Education

edited by
Advanced Chemistry Classroom and Laboratory Joseph J. BelBruno
Dartmouth College
Hanover, NH 03755

Photochemical Kinetics: Reaction Orders and Analogies with

Molecular Beam Scattering and Cavity Ring-Down Experiments
Michael Hippler
Physical Chemistry, ETH Zrich, Zrich CH-8093, Switzerland; hippler@ir.phys.chem.ethz.ch

Photochemical reactions are ubiquitous and relevant; for
example, chemical reactions initiated by absorption of light
are involved as the primary step in the vision process (ab-
sorption of light by a pigment in the eyes receptor cells), in
photosynthesis, and as the driving force in atmospheric chem-
istry. Despite its fundamental importance, photochemical ki-
netics is not often treated in much detail in physical chemistry
courses and textbooks and, as consequence, concepts are of-
ten not well-understood and remain unclear.
Reaction orders of photochemical reactions remain a
subject of debate. In a recent article in this Journal (1), pho-
tochemical reactions were even denied a reaction order. In
this article, we want to emphasize that a photochemical re-
action system is composed of several elementary steps, each
of which has a defined molecularity and reaction order. The
elementary, primary absorption step can be considered a bi-
molecular reaction. Depending on the experimental condi-
tions, the apparent total reaction order of the mechanism may
have different values, but can still be defined in most cases.
The photoabsorption step should be considered a kinetic
elementary reaction. A standard photochemical experiment
with irradiation of a sample with constant light intensity, how-
ever, does not correspond to a conventional kinetic experi-
ment with homogeneous reagent concentrations that react over
time without external perturbations. Possible conceptual dif-
ficulties may be avoided by realizing two analogies between
experiments involving light and kinetic experiments not
involving light: A standard absorption measurement has an
analogy with a molecular beam scattering experiment, and
cavity ring-down spectroscopy has an analogy with a conven-
tional static reactor experiment.
Photochemical Reaction Systems
Many elementary steps are relevant for a typical photo-
chemical reaction mechanism (Table 1). The reaction se-
quence is initiated by absorption of photon by a molecule
A (StarkEinstein law), eq 1. The excited molecule A* may
then undergo a chemical transformation in a unimolecular
elementary reaction, eq 2; for example by dissociation. In
competition, the excited molecule may be quenched by col-
lisions (A* + M A + M) or by spontaneous emission of a
photon (A* A + ). is in general different from the
initially absorbed photon (different wavelength, different
propagation direction). Quenching reactions are summarized
symbolically in eq 3. A* may also react with a photon and
then emit both photons (stimulated emissionsaturation) or
become further excited (two-photon absorption), but these
processes can usually be neglected at moderate photon den-
sities (light intensity). Additional competing elementary re-
actions are collision-induced emission, intersystem crossing,
phosphorescence, internal conversion, or triplettriplet ab-
sorption (2, 3). The simplified reaction scheme, eqs 13, is a
representative example to discuss important aspects of pho-
tochemical kinetics. The net reaction of the photochemical
mechanism is A + = P, eq 4, but in the discussion one has
to bear in mind that different elementary steps are involved,
eqs 13.

Table 1. Simplified Photochemical Reaction Mechanism

Equation Reaction Reaction Rate Lawa

d [ A ]( ) d [ A* ]( )
k1 1 1
d [ ]
(1) A + A* vC(1) = = = = k1 [ A ][ ]
dt dt dt
d [ A* ]( )
k2 2
d [P ]
(2) A* P vC(2) = = = k2 [ A*]
dt dt
d [ A*]( ) d [ A ]( )
k3 3 3
(3) A* A vC(3) = = = k 3 [ A* ]
__________________ dt dt
(4) A + = P
aBrackets denote the number concentration of a species, v are reaction rates (based on number concentration), and k are rate
c
constants. Indices on differentials indicate a contribution to the total change of number concentration from one reaction, in addition to
contributions from other reactions.

1074 Journal of Chemical Education Vol. 80 No. 9 September 2003 JChemEd.chem.wisc.edu


Reaction Orders
The photoabsorption step, eq 1, is clearly a bimolecular
elementary reaction with a total reaction order of two, if one
considers the photon as particle and the absorption process
as an inelastic collision of two particles. The reaction rate of
the bimolecular reaction is vC(1) = k1[A][]. If [] remains con-
stant (irradiation with constant light intensity), the reaction
is pseudo-first order; that is, the apparent total reaction or-
der is one. If, in addition, [A] is only slightly diminishing
during the measurement, for example as a result of low ab-
sorption cross-sections or if [A] is very large, vC(1) may ap-
pear approximately constant. The apparent total reaction
order is then zero. The true total reaction order of a bimo-
lecular elementary reaction, however, is always two.
The most relevant quantity in the reaction mechanism
is the rate of product formation, vC = d[P]dt. According to
eq 2, vC = k2[A*]. To evaluate this rate further, we need an
expression for [A*], which can be provided by the assump-
tion of a quasi stationary-state condition for A* (24). Un-
der normal conditions, thermal population of A* is negligible
and deactivation of A* by reaction or quenching is much
faster than excitation of A by absorption of a photon. With
[A*] << [A], a quasi stationary-state concentration [A*]SS is
rapidly attained in the experiment. Collecting the contribu-
tions from eqs 13 to the total change of [A*] and evaluat-
ing d[A*]SSdt = 0, we obtain [A*]SS = k1[A][](k2 + k3)
and thus
k1 k2
vC = [ ][ A ] = keff [ ][ A ];
k2 + k3
k1 k2 (5)
keff =
k2 + k3
The quantum yield for product formation, P (number of
product molecules P for each photon absorbed), is
vC (2 ) k2 [ A* ] k2
P = = = (6)
vC (1) k1 [ ][ A ] k2 + k3
where [A*]SS has been inserted in the last relation. The effec-
tive total reaction order of the photochemical system is clearly
two.
As discussed before, if in a particular experiment [] or
[A] remain approximately constant during the kinetic mea-
surement, the apparent total reaction order may be one or
zero. The true reaction order is still two. Increasing [] or
[A] in a different experiment increases the reaction rate ac-
cordingly. The apparent order varies for different initial con-
ditions, but this does not mean that the reaction has no
reaction order at all.
Analogy with Molecular Beam Scattering Experiments
In a standard photochemical experiment a sample is
irradiated with constant light intensity. The number con-
centration [] is constant within a small volume element:
Absorbed photons are missing in the light beam leaving
the volume element, but they are replenished from the beam
JChemEd.chem.wisc.edu Vol. 80 No. 9 September 2003 Journal of Chemical Education
Research: Science and Education
entering the volume. [] remains constant in time, but de-
pends on the local absorption path length x. Light intensity
I is defined as incident power (energy per unit time) per unit
area: I = nhcV = hc[], where nV is the number density,
h the photon energy, the frequency, and c the speed of
light. With this relationship, the reaction rate law from eq 1
can be reformulated in terms of intensity instead of number
concentration, dI/dt = k1[A]I. Since light is traveling through
the sample, this equation is valid in a volume element mov-
ing at speed c with the incident light. With the transforma-
tion of c = dxdt to 1dt = cdx, the rate equation for a
stationary point along the absorption path is
dI k1
=
c
[ A ]I (7)
dx
After integration, eq 8 is obtained for the attenuated light
intensity for the absorption path length l,
k1
I (l ) = I 0 exp [A ]l = I 0 exp ( [ A ] l ) (8)
c
where = k1c defines the absorption cross-section. If [A] is
constant along the absorption path, this equation corresponds
to the well-known BeerLambert absorption law (2, 3). If
[A] is known, the measurement of I0 and I(l ) provides the
absorption cross-section and thus the absorption rate con-
stant k1.
In a simple, standard kinetic experiment not involv-
ing light, reactants have a defined and uniform, homogeneous
concentration, which is usually achieved by mixing reactants
and stirring. Concentrations then change uniformly in the
sample volume during the course of reaction. A standard pho-
tochemical experiment therefore does not correspond to a
simple kinetic experiment. Rather it has a close analogy to
a kinetic molecular beam scattering experiment. To study a
bimolecular reaction (A + B products) in a typical mo-
lecular beam scattering experiment (24), molecules A emerge
from a reservoir and pass a velocity selector (Figure 1). The
molecular beam with velocity v and particle flux I0 (particles
per unit area per unit time) then enters a scattering chamber
of length l with target molecules B. By elastic or inelastic scat-
tering (reactions), molecules A are removed or scattered from
the molecular beam. A particle detector after the scattering
chamber thus records an attenuated molecular beam flux I(l ).
Figure 1. Diagram of a typical molecular beam scattering experi-
ment. Areservoir with molecular beam of species A emerging;
Bvelocity selector with slotted disks; Cscattering chamber with
target molecules of species B at pressure p and temperature T,
interaction length l; Dparticle detector. All components are in an
evacuated enclosure.
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 Research: Science and Education

I(l ) is related to I0 by an equation analogous to the Beer

Lambert absorption law (24). By comparison with I0, the
specific collisional cross-section or rate constant is obtained;
this procedure is entirely analogous to the light absorption
measurement described above. If one replaces molecules A
by photons, molecular beam by light beam, scattering
chamber by sample volume, beam velocity v by speed
of light c, et cetera, the analogy of a standard photochemi-
cal experiment with a molecular beam scattering experiment
Figure 2. Diagram of a cavity ring-down experiment. Iincoming
becomes very evident. light from a laser source, switched-off at t = 0; I(t)light intensity
monitored outside the cavity with length l; Mtwo highly reflective,
Analogy of Cavity Ring-Down Spectroscopy concave cavity mirrors.
with Static Reactor Experiments

Cavity ring-down (CRD) spectroscopy is a new tech-
nique to accurately measure weak absorption cross-sections
or to detect trace amounts in analytical applications (5, 6).
In CRD spectroscopy with continuous diode laser sources,
light is coupled into an optical cavity composed of two highly-
reflective mirrors (typically reflectivity R > 99.9%). Within
the cavity, a constant light intensity I0 is rapidly attained in
an equilibrium between gain by light input and loss by ei-
ther imperfect mirrors or as a result of absorption by gas-
phase species inside the cavity. The laser source is then
switched off and light intensity decays within the cavity as a
result of losses on the mirrors and to absorption. A small
amount of light I is always leaking out of the cavity. I(t) is
monitored by a photodiode or photomultiplier; it is directly
proportional to the light intensity I(t) inside the cavity. Since
light is typically reflected back and forth thousands of times
inside the cavity during a decay event, effective absorption
path lengths of several km are easily achieved, which explains
the enormous sensitivity of CRD spectroscopy to the absorb-
ing species (Figure 2; refs 5, 6 ).
After one pass through the cavity of length l from one
mirror to the other, light intensity is attenuated by
I diode is switched off, and the decay of the light intensity is
( ln R + l )
= R exp [ l ] = exp
I0
((1 R ) + l )
exp
length where N2O absorbs light and much slower at a slightly
where ln R (1 R) holds for R 1 (highly-reflective mir-
rors). In eq 9, the BeerLambert absorption law has been
used. The absorption coefficient is = [A] and [A] the num-
ber density of absorbing species A inside the cavity with ab-
sorption cross-section . After n passes,
I n
= (R exp [ l ])
exp
((1 R ) + l ) n
(10)
I0
and substituting n = (ct)l, where c is the speed of light, we
finally arrive at,
c
the root-mean-square noise equivalent absorption coefficient
I (t ) = I 0 exp
(1 R ) + c t
= I 0 exp [k t ];
l
is about 2 108 cm1 (6). This detection limit compares
(1 R ) c
k = + c
l The relationship between the CRD parameters in eqs
where I(t) is the light intensity inside the cavity and I(t) is
the light intensity leaking out of the cavity, which is propor-
tional to I(t). The ring-down constant k is obtained by a
single-exponential fit of the observed decaying light inten-
sity. If the spectral baseline (1 R)cl is determined in a sepa-
rate experiment (empty cavity, without absorbing species A),
the absorption coefficient can be measured, from which
follows the absorption cross-section (if [A] is known) or
the concentration [A] (if is known). In the derivation of
eq 11 it has been assumed that [A] remains approximately
constant with time, and hence = [A]. This is adequate
since CRD spectroscopy is usually applied to measure very
weak absorptions (see below for the more general case where
[A] is not constant). It has also been assumed that both mir-
rors have the same reflectivity R. If they are different (R1 and
R2), a similar derivation shows that R in eq 11 is replaced by
(R1 + R2)2.
As an example, typical decay curves I(t) observed by a
photo diode in the near-infrared spectral region close to 1.3
m (6) are shown in Figure 3. In the experiment, 1 mW
infrared light from a continuous diode laser is coupled into
a cavity composed of two highly-reflective mirrors (R =
99.988%, l = 29.5 cm). The cavity is filled with 0.53 mbar
nitrous oxide gas (N2O) at room temperature. At t = 0, the
observed. The curves are characterized by an exponential de-
(9)
cay with ring-down constant k. The decay is fast at a wave-
different wavelength where N2O does not absorb light (Fig-
ure 3). The 1e decay time of the empty cavity is about 8
s; within that time interval, light makes about 4000 round
trips in the cavity and travels a distance of 2.4 km, which is
a measure for the effective absorption path length. Knowing
the concentration of N2O, k can be converted into the ab-
sorption cross-section . By measuring at different wave-
lengths, an absorption spectrum is obtained. The very weak
rovibronic R(7) transition of the 1 + 33 combination band
of 14N216O near 7788.5 cm-1 obtained with the described
setup (6) is shown in Figure 4. Taking the noise level of the
spectral baseline in Figure 4 as measure for the detection limit,
favorably with other extremely sensitive detection techniques,
(11) for example, frequency modulation diode laser spectroscopy.
911 and the rate constants of the various elementary steps
involved can be derived as follows: if the absorption and pho-

1076 Journal of Chemical Education Vol. 80 No. 9 September 2003 JChemEd.chem.wisc.edu


Figure 3. Two typical decay curves in a CRD experiment after switch-
ing-off a near-infrared diode laser at t = 0. The fast decay corre-
sponds to a wavelength where the N2O inside the cavity absorbs
light (spectrum shown in Figure 4) and the slower decay to a slightly
different wavelength where N2O does not absorb light.
tochemical reaction is described by the simplified mechanism,
eqs 13, and if the quasi stationary-state condition for A* is
applied with the previously defined effective rate constant keff
= k1k2(k2 + k3), we arrive at
d [A ] d [ ]
= keff [ ][ A ] and = k1 [ ][ A ] k4 [ ] (12) reaction. By analogy with molecular beam experiments and
dt dt
Equation 12 is the coupled rate law that applies to the situa-
tion inside the cavity after switching off the external light
source. Mirror losses contribute to the decay of photon den-
sity via the rate constant k4 = (1 R)cl. Light intensity I is
related to photon density [] by I = hc[]. If [A] remains
approximately constant during a CRD measurement, k1[A]
is constant and corresponds to the constant c in eq 11.
Straightforward integration of the differential eq 12 shows
the equivalence between eqs 11 and 12 in this case. Photon
density or light intensity within the cavity is then character-
ized by an exponential decay, which usually applies to CRD
measurements of weak absorptions. In the more general case,
however, where the decrease of [A] by absorption or photo-
chemical reaction cannot be neglected, eq 11 is not valid and
a nonexponential decay will be effective described by eq 12.
Since light is trapped and confined in an optical cavity
and then left to react with molecules (absorption) inside the
cavity, there is a perhaps surprising analogy of a cavity ring-
down measurement with a static reactor experiment in ki-
netics. To make this analogy more evident, we describe the
concepts of a conventional kinetic experiment and compare
them in parentheses to the situation applying to a CRD mea-
surement: At t = 0, the reagents (species A and the reactive
species ) are added and mixed carefully in the reactor (the
cavity), and then the reaction is observed by monitoring the
time-dependent concentration of one reactant (photon den-
sity [] or light intensity I(t)). Losses of the reactive species
on the reactor walls also have to be included in the analysis
(mirror losses, k4). One difference between the two experi-
ments is that mirror losses in a cavity are in general substan-
tial, whereas wall losses in a reactor are often negligible.
JChemEd.chem.wisc.edu Vol. 80 No. 9 September 2003 Journal of Chemical Education
Research: Science and Education
Figure 4. CRD spectrum of the R(7) transition of the 1 + 33 com-
bination band of 14N216O.
Conclusions
A photochemical reaction mechanism is composed of
different elementary reaction steps. The reaction sequence is
initiated by the absorption of one photon by a molecule. This
absorption step can be considered a bimolecular elementary
cavity ring-down experiments, it was shown that photoab-
sorption is a special type of elementary reaction, but can still
be described by standard kinetic concepts. Depending on the
experimental conditions, the apparent total reaction order of
the compound photochemical reaction mechanism may have
different values, but will still be defined in most cases. A pho-
tochemical reaction does therefore have a reaction order in
general.
Acknowledgment
I am grateful to Martin Quack for stimulating
discussions.
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3. Atkins, P. W. Physical Chemistry, 5th ed.; Oxford University
Press: Oxford, 1994.
4. Luckhaus, D.; Quack, M. Gas-Phase Kinetics. In Encyclopedia
of Chemical Physics and Physical Chemistry; Moore, J. H., Spen-
cer, N. D., Eds.; IOP Publishing: Bristol, England, 2001;
Chapters A3.4, B2.5.
5. Cavity-Ringdown Spectroscopy: An Ultratrace-Absorption Mea-
surement Technique; Busch, K. W., Busch, M. A., Eds.; ACS
Symposium Series 720; American Chemical Society (distrib-
uted by Oxford University Press): Washington, DC, 1999.
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