1029/2001JA000122, 2002
Received 3 May 2001; revised 14 September 2001; accepted 17 September 2001; published 9 July 2002.
[1] Electron-impact-induced fluorescence spectra of SO2 in the middle ultraviolet and
visible wavelength regions (200–600 nm) have been measured in the laboratory using a
crossed beam experiment at three electron impact energies. The emission spectra at 8, 18,
and 98 eV exhibit a broad and continuous emission region extending from 225 to near
600 nm with a peak emission close to 330 nm. The quasicontinuous SO2 bands arise
primarily from direct excitation of SO2. At 18 and 98 eV, simultaneous excitation and
dissociation of SO2 produces distinct vibrational bands from SO and from atomic
emission lines from S I, S II, O I, and O II that are superimposed on the SO2 electronic
transitions. The laboratory spectra were compared to green/violet color ratios obtained at
Io by the Galileo Orbiter Solid State Imaging experiment. The laboratory spectra were
also applied to the Cassini Imaging Subsystem to determine which filter combinations are
particularly sensitive to electron energy, if the atmospheric gas present in the auroral
atmosphere is solely or primarily SO2. INDEX TERMS: 0310 Atmospheric Composition and
Structure: Airglow and aurora; 6218 Planetology: Solar System Objects: Jovian satellites; KEYWORDS:
ultraviolet, sulfur dioxide, cross sections, Io, spectroscopy, Galileo
SIA 2-1
SIA 2-2 AJELLO ET AL.: EMISSION SPECTRUM OF SO2 BY ELECTRON IMPACT
Table 1. Spectral Assignment for Electron-Impact-Induced Fluorescence Spectrum of SO2 and Cross
Sections (s) of Selected Transitions
Range, nm Assignment s, 1019 cm2a
2 2 b
1 212.9 S II (5p F 4s D) 0.1 [98 eV]
2 219.0 S I (4s3D 1S) b 0.2 [98 eV]
3 223.7 S II (4f 25 2G) b 0.2 [98 eV]
4 283.5 (MUV1) 21.0c [98 eV],
267.0 [SO (A3 ! X3), 23.8c [18 eV]
SO (B3 ! X3)]
5 267.0 (MUV2) 100 [98 eV],
600.0 ~ ! SO2,
[SO2(ã, Ã, B) 91 [18 eV],
[SO (A3 ! X3)] 135d [8 eV]
SO (B3 ! X3) 60 [98 eV - molecular]
126c [98 eV]
203c [18 eV]
301c [8 eV]
Plus over 100 candidate O I, 40 [98 eV - atomic]
O II, S I, and S II emissionsb
a
Electron impact energy valued given in brackets.
b
From NIST web site (http://physics.nist.gov) list of atomic physics transitions and from [Kiehling et al., 2001].
c
From Ajello et al. [1992b].
d
Estimated from 18 eV/8 eV cross-section ratio of Ajello et al. [1992b].
agreement for the spectral features of the SO+ A2 ! X2r laboratory paper by Kiehling et al. [2001], which measured
band system with a threshold near 20 eV [Murakami et al., proton impact emission cross sections of SO2, has observed
1982]. We can conclude that, if present, these transitions are scores of strong O I, O II, S I, and S II lines without
at least a factor of 10 weaker than the SO emissions. blending from the SO2 quasicontinuum of electronic tran-
[12] Figure 3 shows the location of O I, O II, S I, and S II sitions found in low-energy electron impact emission
atomic lines obtained at 1.8-nm resolution from 360 to 560 experiments. The same strongest features are identified in
nm at 98-eV electron impact energy. Approximately 25 Figure 3 by the peak position. Scores of other weaker
distinct emission features are observed. Each of the O I atomic lines pool together overlaying the MUV2 quasicon-
lines at 394.7, 395.4, 436.8, 503.7, and 533.0 nm mentioned tinuum. In addition, near 220 nm we identify, in Table 1,
by Miller and Becker [1987] is clearly visible. A recent weak emissions from a few S I and S II lines. Miller and
Becker have pointed out that the cross sections to the atomic between the allowed and forbidden transitions. This spec-
lines are individually very small: on the order of 1020 cm2 trum is the basic underlying background spectrum to all
for most features. MUV observations regardless of the electron impact energy.
As the electron impact energy is increased above 10 eV, it is
4. Discussion possible to access more dissociative and ionization states in
SO2, and the emission from excited states of SO adds
[13] The quasicontinuum emission spectrum, MUV2, of distinct molecular bands to MUV2 between 220 and
SO2 arises from a number of singlet and triplet states 400 nm and produces the second strong emission feature,
producing a complexity that is enhanced by perturbations MUV1, with an onset energy of 10.4 eV. The highly excited
UV transitions found in the far ultraviolet (FUV) have upper
states that are the terminal states for the visible cascade
atomic features found in this study. The emission cross
Table 2. Revised MUV2 Emission Cross Sections and MUV2/ sections of the FUV transitions are very intense beginning
MUV1 Color Ratios with the onset of dissociative ionization, typically above
35 eV electron impact energy. The O, O+, S, and S+ cascade
Cross Section, 1019 cm2
emissions produce strong distinct structures on MUV2
Energy, eV MUV1 MUV2 MUV2/MUV1 Ratio
above 35 eV. Pure dissociative excitation begins in the
5 ... 22 ... neighborhood of 20 eV and may weakly affect the spectra
6 ... 42 ...
7 ... 84 ...
in the range of 20– 35 eV [Ajello et al., 1992a]. The most
8 ... 135 ... notable dissociative feature is MUV1, formed from a
8.5 ... 163 ... combination of SO B3 ! X3 and SO A3 ! X3
9 ... 165 ... transitions near 255.0 nm. These bands tend to mostly
10 ... 165 ... enhance the short-wavelength extent of MUV2. The spectral
11 4.40 155 35.2
12 9.32 145 5.6 wavelength distribution in MUV2 is energy dependent. The
13 14.4 137 9.5 peak MUV2 emission shifts from a wavelength of 320 nm
14 17.9 129 7.2 (at 8 eV) to 360 nm (at 98 eV) with the onset of dissociative
15 20.8 119 5.7 ionization.
16 22.9 109 4.8
17 23.4 98 4.2 [14] Currently, major questions raised by observational
18 23.8 91 3.8 measurements concern the identity of the emitting species in
20 25.0 78 3.1 the atmosphere around Io and the distribution function of
22.5 24.8 73 2.9 the exciting particles. Torus electrons can excite S, O, and
25 24.3 70 2.9
27.5 24.1 69 2.9
SO, in addition to SO2. The atmosphere of Io has a large
30 23.9 68 2.8 diurnal variation in SO2 column density and SO abundance
32.5 23.7 66 2.8 with respect to SO2 [Wong and Smyth, 2000]. Three distinct
35 23.4 65 2.8 components make up Io’s MUV/visible aurora. The bright-
AJELLO ET AL.: EMISSION SPECTRUM OF SO2 BY ELECTRON IMPACT SIA 2-5
Figure 4. Electron-impact-induced fluorescence spectra with 3.6-nm resolution of SO2 obtained at nine
electron impact energies ranging from 9 to 100 eV over the wavelength range 200– 450 nm. Calibrated
data points are not smoothed.
est glows are blue glows likely resulting from SO2 emis- thereafter until 100 eV. Since the electron temperature in the
sions [Geissler et al., 1999, 2001] close to the equator near vicinity of Io is dominated by low-energy electrons, the
the sub- and anti-Jupiter points from centers of volcanic MUV2/MUV1 cross section ratio is very diagnostic of
activity, with the red and green glows resulting from atomic energy. We list the MUV2/MUV1 cross-section ratio and
O and Na emission. Direct excitation of SO should be weak the corrected MUV2 cross sections in the energy range of
compared to SO2 emissions known to be abundant in 10– 35 eV in Table 2. We see that the emission cross-section
volcanic plumes. If this is the case, these SO2 emissions ratio is 35.2 at 11 eV, decreasing to 2.9 by 25 eV. In Figure 4
could provide a convenient thermometer for determining the we pictorially show the same energy variation information
temperature of electrons exciting emissions. This possibility obtained from nine calibrated spectra of electron-induced
was indicated by Ajello et al. [1992b], who provided the fluorescence of SO2 over the energy range from 9 to 100 eV.
energy dependence of MUV1 and MUV2. The ratio of By carefully measuring the MUV1 and MUV2 peak inten-
MUV2/MUV1 is monotonically decreasing with increasing sities spectroscopically from Io with the Hubble Space
energy, first very sharply from 10 to 20 eV and very slowly Telescope, for example, the mean electron energy could
be determined. This peak ratio is 1.9 at 18 eV in Figure 1
compared to a cross-section ratio of 3.8 in Table 1.
[15] Color ratios within MUV2, itself, are not as diag-
Table 3. Comparison of Laboratory and Galileo Solid State nostic, because of the complicated wavelength behavior of
Imaging (SSI) Subsystem Green (526.5 – 591.5 nm)/Violet (381.5 – the many underlying transitions at any excitation energy.
426.5 nm) (G/V) Color Ratios We can quantitatively demonstrate this analysis technique
Source Location G/V Ratio
by calculating the monoenergetic 8-, 18-, and 98-eV color
ratios for comparison with the Galileo SSI violet and green
Laboratory 8 eV 0.2
Laboratory 18 eV 0.2 filter response [Belton et al., 1992] and with the Cassini
Laboratory 98 eV 0.41 filters (C. Porco et al., The Cassini Imaging System, manu-
SSI – Io Acala 0.35 script in preparation, 2002,)(hereinafter referred to as Porco
SSI – Io Prometheus 0.45 et al., in preparation, 2002) for an SO2-only atmosphere.
SIA 2-6 AJELLO ET AL.: EMISSION SPECTRUM OF SO2 BY ELECTRON IMPACT
Table 4. Cassini Imaging Subsystem Color Ratios for Electron [17] A recent paper by Oliversen et al. [2001] describes
Impact Excitation of SO2 the distribution function of electrons in Io’s atmosphere as a
Ratio of Filter to UV3 mixture of 5-eV thermal, rapidly varying 30-eV nonthermal,
Cassini Central l and 100-eV nonthermal components. Electron impact exci-
Filter [FWHM], nm 8 eV 18 eV 98 eV
tation of atomic O to the optically forbidden 1S state is very
UV1 260 [40] 0.11 0.15 0.29
UV2 300 [60] 0.48 0.85 0.82
efficient for low-energy electrons. The presence of atomic O
UV3 335 [70] 1.00 1.00 1.00 in the atmosphere would also increase the measured inten-
Blue 450 [150] 0.20 0.30 0.61 sity in the green filter. Even though atomic O is globally
Narrow Blue 440 [30] 0.06 0.08 0.18 distributed [Roesler et al., 1999], its presence is modeled to
Green 565 [145] 0.1 0.1 0.4 be only a minor daytime species in the lower atmosphere
[Wong and Smyth, 2000]. The cross section for production
of the O 1S state has a peak value of 4 1018 cm2 near
The green/violet color ratios for the three energies are 10 eV [Itikawa and Ichimura, 1990]. Finally, direct and
shown in Table 3 compared to particular Galileo observa- dissociative excitations of SO, which models show becomes
tions while Io was eclipsed by Jupiter [Geissler et al., 1999]. the dominant gas near the surface at local midnight, could
The numbers in Table 3 represent the ratios of the signals, in also contribute to the green and/or violet filter signals.
photon counts, received within the FWHM of the respective These cross sections have not been measured. However,
filters. The laboratory ratios at 8 and 18 eV are nearly the contribution to the signal level due to SO from the
identical with a value of 0.2, compared to 0.41 for 98 eV. volcanic activity is suspected to be small compared to
In the wavelength region described inclusively by the violet excitation of SO2 [Geissler et al., 1999]. Thus other con-
and green filters (381.5 – 591.5 nm), the two electron impact stituents, particularly atomic O, may contribute to the green
energies (8 and 18 eV) produce spectra with similar relative SSI intensity.
intensities. The error of the laboratory measurement ratio is [18] Cassini has recently flown by Jupiter, acquiring ISS
25% as a root-sum-square error due to background uncer- images of Io’s aurora. We can use the laboratory spectra to
tainty in the green filter (15%) and in the violet filter (12%), predict the measured color ratios. The predicted ISS Cassini
relative calibration (10%), signal statistics over the band color ratios are given in Table 4 for the MUV/visible filters
pass (10% for green and 5% for violet), and measurement (Porco et al., in preparation, 2002). The ratios are given with
uncertainties and digitization of pressure (1%) and of respect to filter UV3. The abundance of narrow filters, in
electron current (2%). The brightest visible Io aurora glows relation to Galileo, of the imaging system on board Cassini
are closely associated with centers of volcanic activity, for make the spacecraft very sensitive to the detection of the
example, Acala and Prometheus. Geissler et al. [1999] find energetics of the Io aurora. The extension of the Cassini UV
green/violet ratios of 0.35 and 0.45 for Acala and Prom- filter central wavelength of ISS down to 260 nm in
etheus, respectively. Our laboratory experiments show that comparison to the Galileo SSI value of 400 nm makes
an electron energy source impacting on a predominantly Cassini much more sensitive to the SO2 dissociative proc-
SO2 atmosphere could be used to explain the observations. ess, a revelator of electron energy. The absence of signal in
The Galileo filters, however, are not optimally located in a UV1 (diagnostic of MUV1) would indicate the importance
spectral range that discriminates the threshold for excitation of low-energy electrons in the Io auroral atmosphere.
of the spectral region near MUV1, a region that would be
most sensitive to electron energy.
5. Conclusions
[16] Our laboratory experiments cannot detect the long-
lived O 1S state that produces visible radiation at O I [19] (1) There are three distinct energy ranges for pro-
557.7 nm at 8-eV threshold energy. The addition of that ducing different SO2 emission spectra: 4 – 10 eV (MUV2
intensity within the SSI green filter band pass should increase only), 10 –20 eV (MUV2 + MUV1), and >20 eV (MUV1 +
the laboratory model of the green/violet observational ratio. MUV2 + atomic multiplets). (2) The visible tail of the SO2
The excitation cross section of O 1S from SO2 has been fluorescence from electron impact extends to near 600 nm.
recently measured by Kedzierski et al. [2000] to be 2.0 (3) The measured intensity ratio of MUV2/MUV1 from Io
1018 cm2 at 100 eV. In the Galileo green filter band pass our is an electron thermometer. (4) Low-energy electron exci-
experiments show that this region contains 8% of the tation of SO2 by 8- to 20-eV electrons can explain the
emission cross section of MUV2. We estimate a total Galileo SSI filter observations with small contributions
emission cross section of 1.2 1018 cm2 at 100 eV and from SO and O.
1.0 1018 cm2 at 20 eV within the green filter band pass
from the SO2 quasicontinuum, not including O 1S. The O 1S [20] Acknowledgments. The research described in this paper was
cross section falls rapidly with decreasing energy, attaining a carried out at the Jet Propulsion Laboratory, California Institute of Tech-
value of about 5 1019 cm2 near 20 eV. The inclusion of the nology, and was sponsored by NASA Planetary Atmospheres Program
Office, NSF and AFOSR. D.L.H., C.A.T., and O.P.M. are each supported
O 1S cross section in the color ratio calculation would more by a National Research Council Resident Associateship.
than double the laboratory green/violet color ratio at 100 eV, [21] Janet G. Luhmann thanks Paul E. Geissler and another referee for
taking the ratio outside the observed Galileo values. How- their assistance in evaluating this paper.
ever, the inclusion of O 1S cross section in the 20-eV color
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