Absorption cross-sections of atmospheric gases for use in aeronomy

E. HUFFMAN'
ROBERT
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United States Air Force Cambridge Research Laboratory, Bedford, Massachusetts

Received November 21, 1968

The current status of absorption cross-section measurements for aeronomic use is reviewed. Recom-
mended values for the gases 0 2 ,N Z r0, and 0, are given at wavelengths where there is strong atmo-
spheric absorption in the 350&10 A region. A table of absorption and ionization cross-sections at
important solar emission lines is given. The problem of insufficient resolution at some wavelengths is
discussed, and information on photolysis products is given where available.
Canadian Journal of Chemistry, 47, 1823 (1969)

Introduction The Absorption Cross-section

The absorption of solar radiation in the ultra-
violet to soft X-ray region is well established as
one of the most important mechanisms for
creating and maintaining the unique charac-
teristics of the upper atmosphere. As the radiation
is absorbed, new constituents such as ions,
electrons, and atoms are formed, and the intensity
at the absorbed wavelengths is reduced, until at
For personal use only.
The absorption cross-section is defined by the
usual absorption law (Beer-Lambert Law)
[I.] I(v) = Io(v) exp [-o(v)N]
In this expression I(v) is the transmitted intensity,
Io(v) is the intensity incident on the absorbing
gas column, o(v) is the cross-section, and N is the
number of absorbers (molecules or atoms) per

ground level only wavelengths greater than about

2900 A are observed. The pattern of the absorp-
tion is complicated, depending on the variation
of absorption with wavelength for each constit-
uent, the atmospheric composition as a function
of altitude, and the detailed intensity distribu-
tion of the solar spectrum. To understand this
absorption profile, it is necessary to have labora-
tory measurements of the absorption cross-
section, or absorption coefficient, which is a
measure of the total attenuation of radiation at a
given wavelength. This information is useful in
aeronomy both to find the altitudes at which
solar energy is deposited and to evaluate the flux
remaining for further absorption at lower alti-
tudes.
This article reviews the present status of
laboratory absorption cross-section measure-
ments and provides recommended values for
aeronomical problems. Only wavelength regions
and gases particularly important for atmospheric
absorption are discussed in detail. he wavelength
region considered is from roughly 3500 to 10 A.
The gases discussed at length are molecular
oxygen, molecular nitrogen, atomic oxygen, and
ozone. These four gases account for most of the
solar absorption. There are several older reviews
of this general subject (1-3).
'1967-68 address: Department of Physics, Imperial
College, London, England.
cm2 column in the light path. The cross-section o
is generally given in units of Megabarn (Mb),
which is equal to lo-'' cm2. The data may also
be presented as the absorption coefficient k, with
units of cm-'. It is equal to on,. lo-", where o
is in Mb, and Loschmidt's number no, is 2.69 x
1019 cmP3.
The measurement procedure for the absorption
cross-section involves finding I(v) and Io(v) at
known values of v and N. It is only necessary to
measure the ratio I,(v)/I(v) and thus the simpler
relative calibration of the detector is adequate.
For many cases, o(v) as calculated from eq. [ l ] is
constant over a range of N values, and this
cross-section can then be used to calculate the
absorption or the number of absorbing molecules
in atmospheric problems. There are, however,
important cases discussed in a separate section
where the typical laboratory resolution is in-
adequate and various approximate o(v) values
must be given.
No review of the experimental details of the
light sources, monochromators and spectro-
graphs, and detectors used will be given here.
These are covered fully in the references and in
reviews (4) and (5).
The absorption cross-section curve itself pro-
vides little information about products or excited
states formed as a result of the absorption. At
most wavelengths considered here, there are a
 1824 CANADIAN JOURNAL O F
number of possibilities including excitation, dis-
sociation, ionization, dissociative ionization, and
various other combinations of these processes.
The products of dissociation or ionization pro-
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cesses may be left in excited states, and in some
cases these states may become deactivated by
emission of radiation.
In the observed spectrum or cross-section curve,
excitation produces the normal molecular bands
and atomic lines generally measured and classified
in absorption spectroscopy. Dissociation and
ionization processes are indicated by absorption
continua. Diffuse bands or lines are an inter-
mediate case and indicate predissociation or
autoionization processes. In the wavelength range
discussed here, a number of different processes
usually occur at the same wavelength.
The absorption cross-section can be considered
to represent the sum of partial cross-sections of
the various detailed processes. The partial cross-
sections give the fractional amounts of the dif-
ferent products resulting from the absorption.
For personal use only.
For example, the cross-sections for ionized and
non-ionized products can be given. For partial
cross-sections, a quantitative measurement of the
products is required, which generally presents
experimental difficulties. Some processes can
usually be ruled out by energy considerations.
The cross-sections involving photoionization will
be dealt with in a separate paper at this sym-
posium.
The photodissociation cross-section and prod-
ucts are of considerable interest, for both the
major and minor atmospheric gases, but little
detailed information is available. Photochemical
investigations may give information on products
at some wavelengths. A review is available (6)
for many atmospheric gases.
The absorption cross-section is also related to
the oscillator strength of the transition (7), and
the oscillator strength can be obtained directly
from an integration of the observed cross-section
curve at sufficiently high resolution. This aspect
of the subject is not discussed since oscillator
strengths are covered by another paper in this
symposium.
Resolution Problems
The resolution of the spectrometer is generally
not adequate for atomic lines or sharp molecular
bands encountered in the spectrum. Using the
normal procedure given above, the cross-section
CHEMISTRY. VOL. 47, 1969
calculated from [ l ] is not constant but usually
decreases with increase in N, and thus more
detailed consideration must be given before
applying the laboratory measurements to atmo-
spheric problems. The actual cross-section is very
large at the line center and rapidly becomes
weak away from the center. When a measureable
change in transmission is detectable, the narrow,
strongly absorbing center of the line is already
completely absorbed. The change in absorption
with the change in number of absorbers is thus
controlled by the weaker absorption in the wings
of the line. The cross-section thus appears to
become smaller as the amount of gas in the light-
path increases.
The problem may be approached by examining
the typical spectrometer experiment using con-
tinuum background radiation in more detail. The
instrument provided a narrow range of fre-
quencies around the nominal value, and an
absorption measurement is actually made over
this frequency range. If the intensity-frequency
relation of the radiation provided at the exit slit
at a given nominal spectrometer position vo is
F(v), then the result of an absorption measure-
ment will be
The integrations are over the range where F(v)
has an appreciable value. For a continuum back-
ground source, F(v) frequently has an almost
triangular shape and in this case the integration is
effectively between I a, where a is the half-width.
For a light source emitting sharp atomic lines, the
frequency range transmitted is generally less than
the half-width of F(v) and depends on the
excitation conditions in the light source. If o(v) is
constant over the range of frequencies provided
by the spectrometer, the exponential may be
taken outside the integral in eq. [2], and the usual
absorption law eq. [I] results.
For an isolated non-autoionized atomic line,
and ignoring pressure-broadening as usually un-
important under atmospheric conditions, the
shape of the line is due to a combination of
Doppler and natural broadening, which is some-
times called the Voigt profile (7). For oxygen atom
at 300 OK and an imaginary line at 1000 A, the
Doppler half-width is 3.1 x A. The natural
width for an allowed transition (z = s) at
 HUFFMAN: ABSORPTION CROSS-SEIZTIONS OF ATMOSPHERIC GASES
1000 A is 5.3 x A. The typical bandwidth
available is from about 0.5 to 0.05 A. Thus, the
absorption line is much narrower than the band-
width. The values of I(vo)/Io(vo)obtained depend
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on the line shape o(v) and F(v) as shown in eq.
[2], and in general o(v) cannot be evaluated
without some knowledge of the line shape to be
expected.
This problem of obtaining useful information
under conditions of inadequate resolution is a
well-known difficulty in astrophysical and infra-
red investigations, and several procedures have
been developed (7, 8). One technique is to obtain
the integral of the absorption curve over a range
of N. This is called the equivalent width, or
sometimes the total absorption. The equivalent
width W is equal to the following
One can then obtain the "curve of growth" by
plotting W against N. This curve would allow an
For personal use only.
estimate of N to be made if W values were ob-
tained under similar conditions of absorbing gas
environment, since W is independent of resolu-
tion over fairly wide limits (7, 8). The complete
curve of growth for an atomic line is rather
complicated even for an isolated line with only
natural and Doppler broadening. However,
under many conditions the center is completely
absorbed and the strong line approximation is
applicable, which means that W is proportional
to JN. This behavior is found when the line has
a Lorentz shape, which occurs when the absorp-
tion is controlled by the wings of the line. A
demonstration of this effect for sharp 0, bands
has been given (9). Although little absorption
data on atmospheric gases is now presented in
this way, it is suggested that curves of Wagainst N
would be of use in some cases. It will be most
useful when the solar radiation background is a
continuum or when an artificially introduced
continuum light source is used. Difficulties in-
clude partly overlapped lines, unusual auto-
ionization profiles, and molecular bands.
Continuum background light sources are con-
sidered more useful than line sources in general
because they give the absorption curve at all
wavelengths and lead to a more complete under-
standing of the absorption processes. However,
they give difficulty when a solar line of interest
falls at an absorption band or line of the atmo-
1825
spheric gas, since the bandwidth of the con-
tinuum usually employed is much larger than the
solar line half-width. For these cases, one ap-
proach has been to use a light source emitting
lines at the solar wavelengths rather than a
continuum (10). These lines may be much
narrower than the continuum background band-
widths generally available, and thus they more
nearly approximate the solar lines in half-width.
They are also more intense than usual continuum
sources. This is a useful interim procedure, but it
is open to criticism for several reasons. First, the
lines emitted may be quite different from the
solar lines in shape, self-absorption, or relative
multiplet intensities, due to differences in excita-
tion conditions in the sun and in laboratory dis-
charges. In fact, the laboratory lines may be as
much as 0.1 A wide (lo), which is within the
capability of continuum measurements. Further-
more, solar lines from highly ionized atoms are
not usually produced in the typical laboratory
source, so the continuum background must be
used for these cases. Even when using lines, in
some cases where o(v) varies with N using con-
tinuum radiation, a similar variation occurs using
line sources. For further progress, more informa-
tion about the solar line-shapes coupled with high
resolution continuum data is needed. Continuum
sources offer the advantage of improviilg the
resolution in a straightforward way and of
eventually interpreting the data more completely.
These improvements in resolution and in knowl-
edge of the solar line shape are not likely to
become available soon. Thus, both continuum
and line data are valuable to have at the present
time, where a large number of measurements
have not been made at some wavelengths, and
data from both sources is included here.
In conclusion, it is apparent that considerably
more attention must be given to cases where
resolution is insufficient in order to extract the
most information of aeronomic interest from
laboratory measurements. In addition, some
difficulties in comparing photon absorption and
various electron impact experiments might have
been avoided by earlier recognition and discus-
sion of these resolution problems (1 1). Where
resolution is not adequate, information about the
number of absorbing species must be given. This
is now usually given only as a range of values. A
plot of transmission or measured apparent ab-
sorption cross-section for atmosphere values of N
 CANADIAN JOURNAL O F CHEMISTRY. VOL. 47, 1969

TABLE I
N2, and 0 at solar lines
Absorption and ionization cross-section of 02,
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0 2 N2
Solar line h 0
(A) Classification CJ 01 CJ GI CJ =
For personal use only.

NOTE:cross-sections in M b cm2). Values based on data in refs. 1, 10, 17, 23.24, 25, 28,29 , 31, and36.
Table prepared in collaboration with R. I. Schoen.
OBlend of several lines observed in solar socctrum.
bThe absorbing gas has discrete structure'at this wavelength and thus the cross-section presently measurable
given in the table may not be applicable. See text and references.
CConsiderable variation among measurements.
dThese lines not resolved in laboratory cross-section measurement.
LPossible overlap with atomic oxygen ground state (3P) absorption line. See Table 111.
JPossible overlap with atomic oxygen metastable state (ID) absorption line. See Table 111.
 HUFFMAN: ABSORPTION CROSS-SECTIONS OF ATMOSPHERIC GASES 1827
would be of considerably more value. Throughout TABLE I1
this review, regions where the structure has not Absorption cross-sectionsa at wavelengths less
been adequately resolved will be mentioned. than 304 A.
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Wavelengthb (A) O2 Nz 0
Cross-section Measurements
General 247.2 12.3 9.8 6
The following cross-section curves and tables 209.3 9.0 6.5 4
100 1.9 0.84 0.8
are considered to be the best values available at 68 .o 0.9 0.50 0.2-
the present time. In this review, consideration was
given to all published values known to the author.
The wavelength range covers the upper wave-
NOTE:Data primarilyfrom refs. 12,36, and 47. Cross-section
length where appreciable absorption begins to in Mb (10-lacm').
OThese cross-sections are assumed to be equal to the
about 10 A. These values should be useful at ionization cross-section at least to lOOA although there are
nd yield measurements. See also paper by)^. 1. Schoen in this
atmospheric densities, except in wavelength re- symposium.
gions mentioned where resolution is a problem. bThere are a number of solar lines in this region, but there
have been few measurements, and also the cross-section curve
The atmospheric temperature may be consider- appears to be relatively smooth. The wavelengths used should
allow a reasonable estimate to be made.
ably above or below room temperature, but most =This value is one-half the 0, cross-section.
cross-sections are measured at room temperature.
Where data at other temperatures are available, Molecular Oxygen
they are mentioned. The % uncertainties have Molecular oxygen has important absorption
not been estimated, but they are in the range from 2600 A to lower wavelengths. Cross-section
+- 10 % except at lines or bands. data are given in Figs. 1 to 6. Lower wavelengths
For personal use only.

In addition to the gases treated in detail, there are included in the atomic oxygen cross-section
are a number of minor constituents whose curves presented later. Absorption cross-section
absorption cross-sections are of less importance values at the more intense solar lines are given in
in aeronomy. The atomic gases in this category Table I, and Table I1 gives shorter wavelengths.
include H, N, Ar, He, Na etc., and recent reviews In most cases, at least two measurements are
are available (12, 13). Molecular gases include available, and the data are in reasonably good
NO, NO,, N,O, H,O, CO,, CO, H,, CH,, etc. agreement. There are many investigations of the
Data on these gases have been reviewed (1, 13). absorption spectrum given in the references.
The cross-section in regions where the solar The weak Herzberg continuum in the 2600-
radiation largely consists of strong emission lines 1850 A region shown in Fig. 1 is usually con-
is difficult to obtain from published curves. Table sidered as the primary source of oxygen atoms
I lists the total absorption and total ionization below 80 km. In this dissociation process, two
cross-section at these lines from 1215.7 A (H Ly a)
to 304 A (He Ly u). In order to provide a con-
sistent review within this symposium, Table I was
prepared jointly with R. I. Schoen, who discusses
ionization cross-sections in detail in another
paper.
One problem in the application of laboratory
data to atmospheric problems is the unavail-
ability of large-scale cross-section curves. These
are frequently not published even when prepared
because of space limitations in journals. Such
curves are available to aeronomists, by request,
from the author. These curves were prepared in
connection with previous work from this labora-
tory. At present, N, and 0, in the 600-1000 WAVELENGTH IL)
region at a bandwidth of 0.5 A are available. It
is planned to improve these data in wavelength FIG.1. Molecular oxygen absorption cross-sections;
o,, value extrapolated to zero pressure; o,, 1 atrn data,
range and resolution in the near future. ref. (14).
 1828 CANADIAN JOURNAL O F
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O . O O O l ~ o o ~ I 1950 I I I I
WAVELENGTH (i)
FIG.2. Molecular oxygen absorption cross-sections,
Schun~ann-Rungebands, ref. (9).
ground state (3P) oxygen atoms are formed, since
there is not sufficient energy to excite the meta-
stable 'D and IS atoms at these wavelengths.
There are two measurements in fairly good agree-
ment (14, 9). The cross-sections are very small,
and the high pressures necessary result in forma-
tion of some 0, dimer in the cell, so extrapolation
For personal use only.
to zero pressure is necessary.
The Schumann-Runge bands (3C,- + 3Cgf)
between 1750 and 2010 A require high resolution
to obtain accurate cross-sections (1, 9, 15). It is
also difficult to separate the Herzberg continuum
and the Schumann-Runge bands in the 1900-
2030 A region. Absorption data (9) are given in
Figs. 2 and 3, but these are averaged values
because of insufficient resolution. It is likely that cussed (21), and an increase in cross-section with
much experimental work will be done on these
bands in the future with high resolution.
The strong Schumann-Runge continuum
(1250-1750 A) is very important, since it is the
primary source of oxygen atoms at altitudes
greater than 80 km. The cross-section has been
1750 1800 1850 1900
YIAVELENGTH (i)
FIG. 3. Molecular oxygen absorption cross-sections,
Schumann-Runge bands, ref. (9).
CHEMISTRY. VOL. 47, 1969
I I
2000
1300 1400 1500 1600 1700
WAVELENGTH (A)
FIG. 4. Molecular oxygen absorption cross-sections,
Schumann-Runge continuum, ref. (9).
measured repeatedly with photoelectric tech-
niques with generally good agreement (1, 9, 16-
18), and a representative curve (9) is given in Fig.
4. Absorption in the principal continuum is
believed to produce one ground state (3P) and
one metastable (ID) oxygen atom. Evidence
from photochemically induced secondary reac-
tions and from emission has been given for
0('D) production (19, 20), but more direct
observation and quantitative cross-sections are
also needed. A temperature effect has been dis-
temperature has been found in the 1580-1950
region (22).
The spectrum from 1250 A to the ionization
poteiltial at 1027.8 A is very complex (1, 16).
There are several "windows7' of low cross-
section, one of which corresponds almost exactly
to the intense H Ly line. As is well known, this
ionizing radiation can penetrate much deeper into
the atmosphere than nearby wavelengths.
The region 1070 to 600 A shown in Figs. 5 and
6 has been studied several times recently with
continuum sources (23-25) and a line source (10).
The measurements of refs. (25) and (10) are in
best agreement and are given more weight in
Table I. In this region, ionization and dissociation
continua are overlapped by rather diffuse and
generally autoionized bands. The dissociation
continua in this region have recently been given
(25).
Appreciable quantities of the metastable O2
alAg molecule appear to be present in the upper
 HUFFMAN: ABSORPTION CROSS-SECTIONS OF ATMOSPHERIC GASES
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For personal use only.
WAVELENGTH
FIG. 5. Molecular oxygen absorption and ionization coefficients, ref. (25).
atmosphere (26, 27). It is conceivable that ab-
sorption by this molecule may be more significant
than generally realized. Some intense bands
attributed to absorption by the alA,, or less likely
the blC,+, state have been observed recently in
the 830-900 A region, (28, 29), and recent work
has found absorption bands of both the alA, and
the blC,+ states in the 1200-1600 A region (30).
Molecular Nitrogen
The absorption cross-section of molecular
nitrogen at important solar lines is given in
Table I, which is based on several recent investi-
gations (10, 31, 24). Table I1 gives shorter wave-
length data. Cross-section curves obtained with
continuum background sources in the region
600-1000 A are given in Figs. 7 and 8. There is an
extensive literature on the absorption spectrum
which can be traced through the references given.
There is one recent paper on absorption at wave-
lengths less than 600A (32).
Molecular nitrogen has a much smaller ab-
sorption cross-section than molecular oxygen at
1829
(%)
wavelengths longer than 1000 A. The Lyman-
Birge-Hopfield bands and several other forbidden
transitions are present at wavelengths between
1450 and 1000 A, but the maximum cross-
sections measured are less than Mb. The
resolution is also generally inadequate for precise
measurements. There are recent studies on high
temperature absorption in this region (33).
There are no strong pl~otodissociation con-
tinua for nitrogen, which is different from
molecular oxygen. This fact helps to explain why
atomic nitrogen is in very small concentration in
the atmosphere, while atomic oxygen is a major
constituent.
At wavelengths less than 1000 A, there are a
number of strong bands which cannot be mea-
sured accurately with the present resolution. The
curve of Fig. 7 for the 800-1000 A region must be
regarded as approximate within regions of strong
bands (1 1, 34), but it is usefill for illustrating the
general absorption in this region. One interesting
situation is the coincidence of the strong H Ly y
solar line (972.5 A) with one of the nitrogen
 1830 CANADIAN JOURNAL OF
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WAVELENGTH
FIG. 6. Molecular oxygen absorption and ionization coefficients, ref. (25).
bands (35). At wavelengths less than the ioniza-
tion threshold (795.8 A), most bands become
more diffuse because of autoionization, and they
are superimposed on the ionization continuum.
Thus, the curve of Fig. 8 should be more reliable.
Recent unpublished results at Air Force Cam-
bridge Research Laboratories indicate that the
step at 661 A is probably not real. The curve
should be rescaled between 600 and 661 A to
form a smooth curve with the longer wavelength
values.
Atomic Oxygen
The atomic oxygen spectrum consists of the
ionization continuum at wavelengths less than
the threshold at 910.4 A and in addition, line
series converging to limits corresponding to the
electronic states of the ion. In the continuum
region, there is good reason to believe that the
absorption and ionization cross-sections are
identical, in analogy with the ionization continua
of the rare gases (12), except for a few non-
autoionizing series lines. Most of the absorption
CHEMISTRY. VOL. 47, 1969
(i)
lines at wavelengths less than the ionization
threshold are autoionized.
Theoretical (36) and experimental (37, 38)
cross-sections are given in Figs. 9 and 10. Table I
gives cross-sections at important solar lines. Until
quite recently there were no experimental values,
but measurements using two independent tech-
niques have now been published. One technique
uses discharged oxygen, which requires correc-
tion for metastable molecules (37), and the other
uses a beam technique requiring calibration
against hydrogen atom (38). They are in only fair
agreement with each other, but they generally
bracket the theoretical curve. Despite these ex-
cellent experiments, the need for additional
measurements is evident. Tables I and I1 rely
primarily on the theoretical curves. Additional
calculations have recently been published (39).
The large number of atomic oxygen absorption
lines in the ionization continuum has only been
realized recently with the measurement and
classification of a number of these series (28).
Some of the more intense series members are
 HUFFMAN: ABSORPTION CROSS-SECTIONS OF ATMOSPHERIC GASES 1831
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3000

-
-5
I-
Zeooo
-0
!
L
W
LL
0
0

Z
0
t-

g I000
Ul
m
4
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800
L I I I I
8 50
I I I I
900
I I I I
950
I I I I
I

1000
WAVELENGTH ( i1

FIG.7. Molecular nitrogen absorption cross-sections, refs. (31, 17).

N*
A= IT"

I I I I I I 1 I I I I I I I I I I I
600 650 700 750 800

W A V E L E N G T H I:(

FIG.8. Molecular nitrogen absorption cross-sections, refs. (31, 17).

 1832 CANADIAN JOURNAL O F
ATOM
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I 1 I ! I I
fP00 800 700 000
WAVELENGTH 18 )
FIG. 9. Atomic oxygen cross-sections. Curve, ref.
(36); A, dipole length; B, dipole velocity; filled circles,
ref. (37); crosses, ref. (38); dashed line beneath point
indicates absorption line; absorption series, ref. (28).
shown in Fig. 9, and it is clear that the lines used
in some laboratory measurements were absorbed
by oxygen atom lines, leading to high cross-
For personal use only.
section values (40), compared to nearby lines in
the continuum region. If a solar line happens to
overlap one of the atomic absorption lines, the
absorption cross-section for this solar line will be
much larger than the continuum value. The
intensity profile with varying altitude will be
dependent on the details of the two line shapes
involved. Wavelengths where this effect is likely
to be important for strong solar lines are given in
Table I, and Table 111 gives the classification and
additional wavelengths. The recent measure-
ments also give absorption lines from the meta-
TABLE I11
Atomic oxygen lines which may absorb solar lines
Solar line 01 line
(A) (A) Classification Remarks
NOTE: atomic oxygen resonance lines (1302, 1305, 1306 11) not
included. References 28, 29. and 45 give details.
OSolar line known to be broad.
bAtornic oxygen linc broadened by autoionization.
=Theselines known to overlap. See refs. 40 and 37.
CHEMISTRY. VOL. 47, 1969
OXYGEN ATOM
SO
FIG. 10. Atomic oxygen cross-sections. See caption
of Fig. 9. Symbol x represents one-half O2 cross-section,
based o n ref. (37).
stable o('D) and 0('S) states (28), which may be
important under special conditions.
Ozone
Ozone (0,) has important atmospheric ab-
sorption at wavelengths less than 3500 A. The
cross-section curves are given in Figs. 11 and 12.
There have been several measurements in sub-
stantial agreement (41, 42). There is less atmo-
spheric absorption at wavelengths less than
2000 A, because solar radiation of these wave-
lenghs does not penetrate to the altitudes where
ozone is present, so this region is not reviewed.
Although the Hartley continuum in the 2000-
3000 A region (Fig. 11) has the larger cross-
section, the greater solar intensity at wavelengths
greater than 3000 A makes absorption in the
weaker Huggins bands also very important (43).
The cross-section data in the region above
3000 A should be improved in resolution to more
WAVELENGTH (8)
FIG. 11. Ozone absorption cross-sections, ref. (41).
 HUFFMAN: ABSORPTION CROSS-SECTIONS OF ATMOSPHERIC GASES
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For personal use only.
FIG. 12. Ozone absorption cross-sections, ref. (41).
accurately assess its importance. New data in
this region have recently been published (44).
The photodissociation products of ozone are of
considerable interest, since they appear to be one
of the most likely sources of excited oxygen
atoms and molecules. At wavelengths less than
3100 A, it is energetically possible to have 0,
'A,and 0 ' D as products of the ozone photolysis.
The threshold for 0 'D formation is 4100 A, but
the process would also yield a ground state
X3Z,- molecule, which would be a forbidden
transition (6). Discussions of the evidence for
these products from flash and steady state
photolysis have been given (27,45), and a general
conclusion is that 0 'D is much better established
as a primary product than 0, alA,. However,
recent photolysis experiments at 2537 A have
succeeded in observing the 0, nlA, -> X3Z,-
infrared atmospheric bands in emission (49).
The intense metastable 0, absorption bands
between 830 and 900 A previously mentioned
(28) have also been observed in the products of
ozone photolysis at 2537 A (50), which supports
the presence of metastable 0, in the products. It
can therefore be considered as established that
the absorption in this region does yield 0,
a A,, but the efficiency is not known.
Conclusions
There is a substantial body of information
available on absorption cross-sections which may
be used with considerable confidence for aero-
nomic calculations. Continued work is resulting
in a convergence of values from different groups
and techniques although this review notes many
areas where work is needed. Agreement with the
findings of rocket spectrophotometry (46) is also
substantial; however, close interaction between
laboratory and field studies is necessary to further
reduce uncertainties.
Acknowledgments
The author would like to thank Professor W.
R. S. Garton, for making facilities available in
his group during preparatioil of this review.
Illustrations and/or additional comment were
provided by R. B. Cairns, W. Swider, K. Watan-
abe, and F. Matsunaga. Special thanks are due to
Y. Tanaka and J. C. Larrabee for discussions
over a period of many years.
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Absorption in the spectral range of the Schumann-Runge bands

M. ACKERMAN, AND M. NICOLET
F. BIAUME,
Znstitut D'Ae'ronomie Spatiale de Belgique 3, Avenue Circulaire, Bruxelles 18, Belgique
Received November 21, 1968

Absorption of silicon lines by O2 in the Schumam-Runge bands has been measured. The results
lead to some conclusions about the nature of the absorption and about the general behavior of the
spectrum.
Canadian Journal of Chemistry, 47, 1834 (1969)

Introduction Runge bands (1750-2000 A) and in the Herzberg

Early measurements, presented in Fig. 1, of the continuum (h < 2424 A) were mainly performed
absorption coefficient of oxygen in the Schumann- with light sources providing spectral emission