Quantum Yield for O(1D) Production from Ozone Photolysis in the Wavelength Range of 193-225 nm

Article abstract of DOI:10.1021/jp049979r

The quantum yield values for O(¹D) production from the photodissociation reaction of O₃ between 193 and 225 nm at 298 ± 2 K are reported. The O(¹D) photofragments have been detected directly using a technique of vacuum ultraviolet laser-induced fluorescence spectroscopy at 115.22 nm which is associated with the electronic transition of O(3s¹D^° - 2p¹D). It has been found that the O(¹D) quantum yield values decrease monotonically as the photolysis wavelength becomes shorter from 0.90 ± 0.12 (225 nm) to 0.48 ± 0.03 (193 nm). Photodissociation processes of O₃ around 210 nm and its atmospheric implications have been discussed.

Full text of DOI:10.1021/jp049979r

2710
J. Phys. Chem. A 2004, 108, 2710-2714
1
Quantum Yield for O( D) Production from Ozone Photolysis in the Wavelength Range of
93-225 nm
1
Satoshi Nishida, Fumikazu Taketani, Kenshi Takahashi,* and Yutaka Matsumi
Solar-Terrestrial EnVironment Laboratory and Graduate School of Science, Nagoya UniVersity,
Honohara 3-13, Toyokawa, Aichi, 442-8507, Japan
ReceiVed: January 1, 2004; In Final Form: February 4, 2004
1
The quantum yield values for O( D) production from the photodissociation reaction of O
2
3
between 193 and
1
25 nm at 298 ( 2 K are reported. The O( D) photofragments have been detected directly using a technique
of vacuum ultraviolet laser-induced fluorescence spectroscopy at 115.22 nm which is associated with the
electronic transition of O(3s D° - 2p D). It has been found that the O( D) quantum yield values decrease
monotonically as the photolysis wavelength becomes shorter from 0.90 ( 0.12 (225 nm) to 0.48 ( 0.03 (193
nm). Photodissociation processes of O
1
1
1
3
around 210 nm and its atmospheric implications have been discussed.
Introduction
TABLE 1: Thermochemical Threshold Wavelengths (nm)
for Photodissociation Pathways of O
3
Photodissociation reaction of O3 in the ultraviolet (UV) region
has been extensively studied due to its pivotal role in the Earth’s
3
-
1
1
+
3
+
3
-
3
O2(X Σg ) O2(a ∆g) O2(b Σg ) O2(A Σu ) O2(B Σu ) 2O( P)
3
O( P)
1180
410
234
590
310
196
460
260
179
230
167
129
170
150
108
198
atmosphere and the fundamental interest on the photochemical
1
properties of the simple polyatomic molecules.1,2 The UV photo-
O( D)
1
O( S)
absorption spectrum of O3 shows a broad feature with a maxi-
-
17
2
-1 3-5
mum around 255 nm (σO3 ) 1.1 × 10
cm molecule ),
means of a technique of resonance fluorescence using an oxygen
and the strong absorption band between 205 and 310 nm is
called a Hartley band. The photodissociation reaction in the
Hartley band gives rise to two different pathways mainly:
11
atom resonance lamp. Stranges et al. photolyzed the O3
molecular beam and studied the multiple-channel dissociation
dynamics using a technique of photofragment translational
spectroscopy. They estimated that the branchings for channels
3
3
-
g
3
3
1
O + hν f O( P) + O (X Σ )
(1)
(2)
of O( P) + O2(X), O( P) + O2(X, vibrationally hot), O( D) +
3
2
1
1
1
-
3
O2(a ∆g), O( D) + O2(b Σg ), and 3O( P) to be 16.8, 7.7, 45.5,
23.3, and 2.0%, respectively, and the rest of the branchings
1
1
O + hν f O( D) + O (a ∆ )
3
2
g
12
was not definitely assigned. Very recently, Takahashi et al.
1
detected the O( S) atoms from the 193-nm photodissociation
of O3 using a technique of vacuum UV laser-induced (VUV-
LIF) fluorescence at 121.76 nm and determined its quantum
At the blue side of the Hartley band, the photoabsorption cross
-
19
2
sections show a minimum around 201 nm (3.1 × 10
cm
-
1 4
molecule ) and increase again as the wavelength becomes
shorter, indicating that a new absorption band starts. For instance
at 193 nm, 10 different dissociation pathways after photoexci-
-3
yield of 2.5 ((1.1) × 10 . The quite small quantum yield value
1
1
3
for O( S) formation indicates that O( D) and O( P) are dominant
photoproducts in the photolysis of O3 at 193 nm. Cooper et
6
tation are thermochemically available as listed in Table 1.
Among the photoproducts, the chemical reactions of O( D)
atoms with small atmospheric molecules are quite important
for understanding the photochemical processes of the Earth’s
atmosphere. Therefore, there have been several reports on the
1
3
1
1
al. detected the O( D) atoms from the photodissociation of
O3 between 221 and 243.5 nm by observing the weak
fluorescence at 630 nm which is associated with the spin-
forbidden D2- P transition. The reported O( D) quantum yield
values lay in the range 0.87-0.88. At wavelengths between 193
and 221 nm, however, there has been no report on measurements
1
3
1
1
experimental determinations of the quantum yield for O( D)
production in the UV photolysis of O3 between 221 and 330
1
1
,2,7-9
1
of the quantum yield values of O( D) production from O3
nm.
Those experimental studies showed that the O( D)
photolysis.
quantum yields between 230 and 300 nm are almost independent
of the photolysis wavelength with an average value of 0.91,
while those above 300 nm decrease drastically as the photolysis
9
In this paper, we report the experimental measurements of
1
the O( D) quantum yields from the photodissociation of O3 at
1
1
,2,7
225, 220, 215, 210, 206, and 193 nm. The O( D) photofragments
wavelength becomes longer, ranging from 0.91 to 0.08.
Turnipseed et al.10 measured the O( D) quantum yield from O3
1
were detected directly using VUV-LIF spectroscopic techniques
and the relative LIF signal intensities were calibrated to
photolysis at 222 nm to be 0.87 ( 0.04, which is close to the
1
1
determine the O( D) quantum yield by two methods as described
average O( D) quantum yield value of 0.91 between 230 and
1
3
below. All the experiments were performed at 298 ( 2 K.
300 nm. They also reported the O( D) and O( P) quantum yields
Photodissociation processes of O3 in the deep-UV region around
at 193 nm to be 0.46 ( 0.29 and 0.57 ( 0.14, respectively, by
1
2
10 nm have been discussed based on the O( D) quantum yields
obtained in this work. Implications of the present results for
stratospheric ozone chemistry are also discussed.
*
Corresponding author. E-mail: kent@stelab.nagoya-u.ac.jp. Fax:
+
81-533-89-5593.
1
0.1021/jp049979r CCC: $27.50 © 2004 American Chemical Society
Published on Web 03/17/2004

1
Quantum Yield for O( D) Production
J. Phys. Chem. A, Vol. 108, No. 14, 2004 2711
Figure 1. Schematic diagram of the experimental setup used in this
1
study, depicting the system to measure the O( D) quantum yields from
Figure 2. Photolysis laser power dependence of the signal intensity
1
ozone photolysis at 206-225 nm. For measurements of the O( D)
1
of O( D) from the 193 nm photolysis of N
2
O (upper panel) and O
3
quantum yield at 193 nm, an Excimer laser was used instead of the
tunable photolysis light source of an OPO laser that was pumped by a
Nd: YAG laser (see text). The excimer laser is not depicted in this
Figure. PM: power meter, ND: neutral density optical filter, BBO:
1
(
lower panel) under the same experimental conditions that the O( D)
1
quantum yield was measured. The O( D) atoms were detected by laser-
induced fluorescence (LIF) at 115.22 nm which is associated with the
1
1
O(3s D° - 2p D)) transition. Straight lines indicate the results of linear
2 4
â-BaB O crystal, and PC: personal computer.
least-squares fit analysis.
Experimental Section
calorimeter (Scientech, AC50UV) by inserting its detector head
into the photolysis laser beam path in front of the reaction cell
after every LIF measurement. An excimer laser operated with
an ArF mode was also used as a photolysis radiation at 193 nm
The experimental setup used in this study was almost same
as that in our previous studies about O3 photochemistry.
Figure 1 shows a schematic diagram of the experimental setup
which was used in the present study. All of the experiments
were performed at 298 ( 2 K. The O( D) photofragments
9
,12,14
(Lambda Physik, COMPex 102) instead of the OPO laser. The
1
excimer laser is not depicted in Figure 1.
produced in the UV photolysis of O3 were detected directly by
using a VUV-LIF technique. The probe laser beams for the
The time delay between the photolysis and probe laser pulses
was controlled by a pulse generator (Stanford Research, DG535),
which was typically set to be 100 ns. The LIF signal was
detected along the vertical direction, orthogonal to the propaga-
tion direction of both the photolysis and probe laser beams, by
a solar-blind photomultiplier tube (EMR, 541J-08-17). The
fluorescence detection direction was parallel to the electric
vector of the photolysis laser and perpendicular to that of the
probe laser. This photomultiplier tube was equipped with a LiF
window and a KBr photocathode and has its sensitivity only in
the wavelength range of 106-150 nm. The output from the
photomultiplier was accumulated using a gated integrator
(Stanford Research, SR-250) over 10 shots of photolysis laser
pulses and stored on a personal computer.
1
1
O(3s D°-2p D) transition at 115.22 nm were generated by the
1
5
phase-matched frequency tripling in the Xe/Ar mixture. The
UV laser around 345.6 nm from an XeCl excimer laser pumped
dye laser (Lambda Physik, COMPex 201 and FL3002E) was
focused into a cell containing a Xe/Ar mixture (10 Torr/200
Torr). Typical pulse energy of the UV laser was 6 mJ. The VUV
photons at 115 nm were introduced into a reaction chamber
through a LiF window that separated the Xe/Ar cell and the
reaction chamber. A part of the generated VUV photons was
reflected into a photoionization cell containing 2 Torr of nitric
oxide (NO) by a thin LiF plate. By monitoring the photoion-
ization current from the NO cell, relative intensity variations
of the VUV laser were measured.
The O gas was produced by passing ultrapure O (Nagoya
3
2
The photolysis laser beam which was tunable between 206
and 230 nm was obtained by frequency doubling of the signal
light from an Nd:YAG pumped optical parametric oscillator
Kosan, 99.9995%) through an ozonizer. The reaction chamber
was evacuated by a rotary pump and a mixture of O3/He was
slowly fed into the chamber through the poly(tetrafluoroethyl-
ene) needle valve. The total pressure in the chamber was
maintained to be 1.0 Torr and the partial pressure of O3 was
about 3 mTorr. The total pressure was measured with a
capacitance manometer (MKS, Baratoron 220) during the
experiments. The partial pressure of O3 in the chamber was
monitored by absorption spectrometry at 253.7 nm using a low-
pressure mercury pen ray lamp. It should be noted that the high
(OPO) laser (Continuum, Powerlite 8010 and Panther OPO) in
a â-BaB2O4 (BBO) crystal. Dichloic mirrors were used to
separate the fundamental and UV outputs. The bandwidth of
-
1
the UV radiation was ∼6 cm (fwhm). The wavelength
calibration of the OPO signal light was achieved simultaneously
1
with measurements of the O( D) spectra by introducing a part
of the OPO signal light into a wavemeter (Coherent, Wave-
master). Typical pulse energy of the UV photolysis radiation
was 0.4-1 mJ. During the experiments, the UV laser power
was monitored on a shot-by-shot basis using a pyroelectric laser
power meter (Molectron, J4-09). A part of the UV photolysis
laser was reflected by a thin fused silica plate onto the power
meter. We also monitored the photolysis laser power with a
1
sensitivity of the VUV-LIF technique allows detection of O( D)
atoms at such low pressures and at short pump-probe delay
1
times and that secondary reactions of O( D) can be ignored.
1
For example, the rate constant for O( D) + O2 reaction was
-
11
3
-1 -1
8
reported to be 4.0 × 10 cm molecule
s
at 298 K, which
was so slow that it could not interfere with the measurements

2712 J. Phys. Chem. A, Vol. 108, No. 14, 2004
Nishida et al.
under our experimental conditions. Helium used as a buffer gas
1
16
was an inefficient quencher for O( D).
We checked the photolysis laser power dependence of the
1
LIF signal of O( D) atoms, and the typical results are shown in
1
Figure 2. Figure 2 shows the plots of the LIF intensities of O( D)
produced from the photodissociation of O3 and N2O at 193 nm
as a function of the 193-nm laser power. It was found that the
1
O( D) LIF signal intensity was linearly dependent on the
photolysis laser at all photolysis wavelengths studied here under
our experimental conditions. Furthermore, no LIF signal of
1
O( D) was observed when the photolysis laser was turned off.
These results indicate that both the multiphoton absorption of
1
O3 to produce O( D) and the photodissociation reaction of O3
around 115.22 nm could safely be ignored under our experi-
mental conditions.
1
Figure 3. Quantum yields for O( D) production in the photolysis of
at 193, 206, 210, 215, 220 and 225 nm. The present results are
O
3
Results and Discussions
indicated by filled circles, in which the error bars are 1σ statistical
uncertainties (see text). For comparison, the former results by Takahashi
et al. (open rhombus), Turnipseed et al. (open circle) and Cooper et
al. (open triangle), are also indicated.
Since the LIF measurements provide only relative concentra-
tions of the species detected, the calibration of the LIF intensities
is needed to obtain their absolute quantum yield values. In our
present study, two different ways of the LIF intensity calibration
were performed to determine the absolute quantum yield values
9
10
13
by Doppler effects due to the partitioning of the excess energy
to the translational motion in the phtodissociation process of
O . The O( D) quantum yield at 230 nm has recently been
reported to be 0.910 ((0.019) by Takahashi et al., which was
1
of O( D) production from O3 photolysis in the UV region. For
1
1
the O( D) quantum yield determination at 193 nm, photodis-
3
9
1
sociation reaction of N2O at 193 nm to produced O( D) was
used as a reference in the present study. Thus, the absolute
quantum yield values at λ ) 206, 210, 215, 220, and 225 nm
were determined by the LIF intensity ratio measurements, using
the following expression:
utilized as a reference:
1
N O + hν (193 nm) f O( D) + N
(3)
2
2
The known concentrations of N2O molecules and O3 molecules
were photolyzed alternatively at 193 nm, and the LIF signal
intensities of O( D) produced photolytically were directly
S (λ) I(230) σ (230)
1D
1D
O3
O3
Φ
O3(λ) ) Φ O3(230) ×
1
(5)
SO3(230) I(λ) σ (λ)
O3
detected by the VUV-LIF technique. The probe laser wavelength
1
1
was scanned over the O(3s D°-2p D) transition, which was
broadened because of partitioning of the available energy. By
comparing the peak area of the fluorescence excitation spectra
where Φ1DO3(230) is the O( D) quantum yield at λ ) 230 nm,
SO3(λ) is the O( D) LIF intensity from O3 photolysis at the
photolysis wavelength of λ, and I(λ) is the photon flux of the
1
1
1
of O( D), SO3(193) and SN2O(193), from the photodissociation
UV photolysis laser. The cross-section values for O3 absorption
1
of O3 and N2O at 193 nm, the quantum yield for O( D)
4
were taken from the report by Malicet et al.
production from O3 photolysis at 193 nm, Φ1DO3(193), could
Figure 3 shows the results of the present study to determine
the O( D) quantum yield from the photodissociation of O3,
be derived using the following expression,
1
1
D
Φ
O3(λ), at photolysis wavelengths of λ ) 193, 206, 210, 215,
1
D
N2O
S (193) × σ (193) × [N O] × Φ
220, and 225 nm at 298 ( 2 K, together with those of former
1
D
O3
N2O
2
Φ
O3(193) )
10
studies by Turnipseed et al. (193 and 222 nm), Cooper et
S
(193) × σ (193) × [O ]
N2O
O3
3
1
3
9
(4)
al. (221 nm), and Takahashi et al. (230 nm). Table 2 lists the
1
quantum yield values of the O( D) production from O3 pho-
in which [N2O] and [O3] indicate the number density of those
molecules in the chamber, and σO3(193) and σN2O(193) are the
tolysis in the wavelength range of 193 and 225 nm. The quoted
uncertainties of the presently determined values (Figure 3 and
Table 2) include the statistical errors (1σ) of the LIF intensity
measurements and the systematic errors estimated for the
pressure and laser power measurements. For the LIF intensity
ratio measurements, 5-20 sets of the experiments were
performed at each photolysis wavelength.
-
19
room-temperature absorption cross sections of O3 (4.28 × 10
2
-1 8
-20
2
-1 8
cm molecule ) and N2O (8.95 × 10
cm molecule ) at
1
1
3
93 nm. The quantum yield for O( D) production in reaction
, Φ N2O, is very close to unity (Φ N2O ≈ 1), because other
1
D
1D
8,17,18
processes are minor.
1
1
For determination of the quantum yields for O( D) formation
from O3 photolysis at 206, 210, 215, 220, and 225 nm, the ratios
of the O( D) LIF intensities at those photolysis wavelengths
At 193 nm, the O( D) quantum yield obtained in this work
is in excellent agreement with that reported by Turnipseed et
1
10
al. within the experimental uncertainties, as shown in Figure
relative to those at 230 nm were measured. Because the
absorption cross sections of N2O were very small at these
wavelengths, N2O gas could not be used as a reference for O( D)
3 and Table 2, while the quoted error for our result is
1
1
significantly smaller than theirs. Stranges et al. estimated the
1
1
1
1
channel branchings for O( D) + O2(a ∆g) and O( D) + O2-
1
+
quantum yield determinations as done for the 193-nm experi-
ments. The photolysis laser wavelengths were alternatively
changed between each of the five wavelengths and 230 nm,
(b Σg ) to be 0.455 ( 0.025 and 0.233 ( 0.020, respectively,
for the O( D) formation processes in the photolysis of O3 at
1
193 nm. Their branching ratios were calculated from the analysis
of the translational energy distribution of the oxygen atom
fragments with a mass spectrometer, although their method
could not detect the O atom fragments quantum-state selectively.
1
while detecting the O( D) atoms produced photolytically by the
VUV-LIF technique. The probe laser wavelength was scanned
1
1
over the O(3s D°-2p D) transition line, which was broadened

1
Quantum Yield for O( D) Production
J. Phys. Chem. A, Vol. 108, No. 14, 2004 2713
1
TABLE 2: Quantum Yields for O( D) Production in the
new electronic surface crossing can be reached above the photon
energy of 230 nm on the 1 B2 surface and then O3 molecules
Ultraviolet Photolysis of O
2 K
3
between 193 and 225 nm at 298
1
(
switch their surface through the new crossing and produce the
1
3
3 -
O( D) quantum yield
O( P) + O2(X Σ g) products preferably.
a
this workb
The latest NASA/JPL panel recommends the temperature-
λ, nm
references
1
D
independent value of Φ O3(λ) ) 0.90 at λ < 306 nm and the
1
2
2
2
2
2
2
2
2
2
93
06
10
15
20
21.5
22
25
28.5
30
0.48 ( 0.03
0.69 ( 0.11
0.72 ( 0.10
0.78 ( 0.10
0.88 ( 0.14
0.46 ( 0.29c
short wavelength limit for the recommendation is not given
8
exactly. However, as shown in Figure 3, the present study
indicates that the NASA/JPL recommendation is not valid in
1
the range of 193-220 nm. For use of the O( D) quantum yield
0.87 ( 0.04c
0.87 ( 0.04d
data in the atmospheric studies, we suggest a simple expression
1
D
to derive the Φ O3(λ) values in the wavelength range of 193-
225 nm as a function of photolysis wavelength λ:
0.90 ( 0.12
0.83 ( 0.04d
0.910 ( 0.019e
1
D
-2
a
. b Quantum yield values for O( D)
1
Φ
O3(λ) ) 1.37 × 10 × λ - 2.16
(6)
Photolysis wavelength of O
production from O photolysis, as determined in the present work. The
3
3
quoted uncertainties include the statistical errors (1σ) of the LIF intensity
measurements and the systematic errors estimated for the pressure and
laser power measurements. Reference 10. Reference 13. The O( D)
quantum yield at 230 nm, which was reported by Takahashi et al.,9
is used as a reference value to obtain the quantum yield values at
This expression was obtained by linear least-squares fit analysis
1
of the present experimental data of the O( D) quantum yield
c
d
e
1
values.
1
We estimated the differences in the stratospheric O( D)
production rates calculated with the constant value of Φ1DO3-
2
06-225 nm (see text).
(
λ) ) 0.90 (NASA/JPL recommendation) and with the wave-
1
1D
1
The total of their branching ratios for the O( D) formation
length-dependent Φ
production rate from O photolysis is defined as follows:
3
(λ) value given by eq 6. The O( D)
O3
20
processes (0.688 ( 0.045) is larger than the values of
1
1
D
D
Φ
Φ
O3(193) ) 0.48 ( 0.03 determined in this work and of
10
1D
1D
O3(193) ) 0.46 ( 0.29 reported by Turnipseed et al. The
J
)
∫
σO3(λ)Φ O3(λ)F(λ) dλ
(7)
reason for the difference is not clear.
The present paper provides the first determination of the
quantum yield values for O( D) production from O3 photolysis
in the wavelength range of 193 and 222 nm. Our results suggest
that the O( D) quantum yield decreases monotonically as the
photolysis wavelength becomes shorter from 220 to 193 nm.
Above 198 nm, the sum of the quantum yields for O( P), O( D),
and O( S) productions should be unity (Table 1). In our present
study, we determined the O( D) quantum yield values at 206,
In eq 7, F(λ) is the altitude-dependent actinic flux. The partial
1
1D
J
values at λ ) 193-220 nm account for 3.0, 4.6, and 2.2%
of the total J values in the whole wavelength region of 193-
35 nm at 20, 30, and 40 km altitudes, respectively, in which
1D
1
3
3
the σO3 values at 295 K reported by Molina and Molina and
3
1
21
the F(λ) values at solar zenith angle (SZA) of 40° are used.
1
1D
Thus, the total J values estimated with eq 7 are smaller than
1
those obtained with the NASA/JPL recommended constant value
2
10, 215, 220, and 225 nm. A very recent study by Takahashi
et al. has revealed that the quantum yield for O( S) production
1D
of Φ O3(λ) ) 0.90 by 0.7, 1.0, and 0.5% at 20, 30, and 40 km
12
1
altitude, respectively.
-
3
is as small as 2.5 ((1.1) × 10 even at 193 nm. Therefore,
It is interesting to refer to Houston and co-workers’ work22-24
the values of 1 - Φ1D(λ) above 198 nm should closely agree
related to the “ozone deficit” issue, which implicates the
discrepancy between the modeled and observed O3 abundance
in the stratosphere. They suggested that the formation of the
3
with the quantum yields for O( P) formation in the photodis-
sociation reaction of O3 between 198 and 234 nm, in which the
wavelength of 234 nm is the thermochemical threshold for O( S)
1
3
-
highly vibrationally excited O2(X Σg , V′′ g 26) from the UV
formation as listed in Table 1.
photolysis of O3 could partly account for the ozone deficit issue
1
A decrease trend of the O( D) quantum yield from 220 to
93 nm is in contrast to the almost constant values of the
3
-
through the possible reactive scattering of O2(X Σg , V′′ g 26)
1
by O2:
quantum yield between 220 and 300 nm. This is attributable to
the different dissociation dynamics of O3 after photoexcitation
at the blue side of the Hartley band and in the center of Hartley
3
3
-
O + hν (λ e 243 nm) f O( P) + O (X Σ , V′′ g 26) (8)
3
2
g
1
band. Many studies showed that the upper 1 B2 excited
3
-
3
-
O (X Σ , V′′ g 26) + O (X Σ , V′′ ) 0) f
2,19
2
g
2
g
electronic state is responsible for the Hartley band transition.
1
3
O (X A ) + O( P) (9)
In the wavelength region of 230-300 nm, about 91% of the
3
1
1
photoexcited O3 molecules dissociate directly to the O( D) +
1
1
3
3
-
O2(a ∆g) products on the surface of the 1 B2 state, while the
2
× {O( P) + O (X Σ ) + M f O + M}, M ) N , O
2
g
3
2
2
residual 9% switch their potential surface to the R state and
(10)
3
3
-
1,2,9
dissociate to the O( P) + O2(X Σ g) products.
Both the
14
3
-
Doppler spectroscopy and the photofragment translational
spectroscopy revealed that the fragment recoil anisotropy from
the 193-nm photolysis of O3 was different from that expected
Net: 3O (X Σ ) + hν f 2O
3
(11)
2
g
11
3
-
The formation of O2(X Σg , V′′ g 26) in the UV photolysis of
O3 (reaction) has been reported by several groups.
1
22,23,25-27
from the prompt dissociation from the 1 B2 state. At the blue
side of the Hartley band, other mechanisms may account for
Although no experimental evidence of the O3 production in
reaction 9 has been reported, the production efficiency of O3
from reactions 8-11 in the stratosphere has been estimated.2
Their estimation is based on the measured branching ratio
between O( P) + O2(X Σg , V′′ g 26) and O( P) + O2(X Σg ,
V′′ < 26) and on assumption that the total quantum yield for
1
3
the branching ratio for O( D)/O( P) productions in the photolysis
of O3 between 193 and 220 nm. One possible mechanism is
that the O3 molecules are photoexcited to an electronic state
2-24
1
3
3
3
-
3
3
-
other than the 1 B2 state and dissociated preferably to the O( P)
+
3
-
O2(X Σ g) products. Another possible mechanism is that a

2714 J. Phys. Chem. A, Vol. 108, No. 14, 2004
Nishida et al.
3
O( P) production in the UV photolysis of O3 is 0.1 between
(9) Takahashi, K.; Hayashi, S.; Matsumi, Y.; Taniguchi, N.; Hayashida,
S. J. Geophys. Res. 2002, 107, 10.1029/2001JD002048.
1
93 and 243 nm. However, our present study clearly indicates
(
10) Turnipseed, A. A.; Vaghjiani, G. L.; Gierczak, T.; Thompson, J.
3
1D
that the O( P) quantum yield ()1 - Φ O3(λ)) in the λ e 225
nm region is larger than 0.1, as shown in Figure 3 and Table 2.
Therefore, it is likely that the stratospheric O3 production due
to eqs 8-11 is more efficient than that estimated previously by
Houston and co-workers.
E.; Ravishankara, A. R. J. Chem. Phys. 1991, 95, 3244.
(11) Stranges, D.; Yang, X.; Chesko, J. D.; Suits, A. G. J. Chem. Phys.
1995, 102, 6067.
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07, 9368.
13) Cooper, I. A.; Neill, P. J.; Wiesenfeld, J. R. J. Geophys. Res. 1993,
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(14) Takahashi, K.; Matsumi, Y.; Kawasaki, M. J. Phys. Chem. 1996,
00, 4084.
15) Hilbig R.; Wallenstein, R. Appl. Opt. 1982, 21, 913.
(
1
9
1
(
Acknowledgment. The work was supported by Grants-in-
Aid from the Ministry of Education, Culture, Sports, Science
and Technology, Japan. The Sumitomo Foundation is also
gratefully acknowledged for financial support.
(
(
(
16) Heidner, R. F., III; Husain, D. Int. J. Chem. Kinet. 1974, 6, 77.
17) Nakayama, T.; Takahashi, K.; Matsumi, Y.; Taniguchi, N.; Ha-
yashida, S. J. Geophys. Res. 2003, 108, 10.1029/2003JD003709.
(18) Nishida, S.; Takahashi, K.; Matsumi, Y., Taniguchi, N.; Hayashida,
S. J. Phys. Chem. A. in press.
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