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The O2(C3Δua1Δg) band system
TfIle spectmscup_v ‘?f tile ru~tlLlst.!bfs stair‘s of 0, has pramted intcrestkg md Liustraring probfems~0 workers ir: rile field hr ssreraf dcc-adcs. Tile st~tcs iu qIwsIi0n i1ax2 been those rirrcr smces corrclaririg wit!1 gr0Imd
_
staw
cItoms
md
I) ir1g lxtw3m
4 mlf
5 CL’
abotc ihc ground skew. dcsQn;rrcd c’X, _ C 31u. and .\‘Xz_ Tlicsc st3tes_ fikc tfw two fokcr :uet.tstzhfes_ a11 andb “5. do net to 3 first ;Ipprosimarion interact Zill* tic11 Afwr or tits S ‘_‘z ground stitfc, and thus transitions bct\\ecn thcsc s% sf3tcs imolvc radirttive fiktimes in tfw rsnge of fO-1IO-’ s [ 1 .?I_ It is for tfds rcason fht progress Ims been sforv botfl in the spcutrosclopy of the tmnsitions and in tile kinetics of the individual states_ Afthough tile A 3XE + _X3X, trmsition has been known for many years in borh ab sorption [3J and emission [3J. not even for tflis systern are adccfuatc kinetic data for tflc upper sf;ltc zlvzilrtbk, zdtflougfl tfle transition is ofparticuhr importance in the cartfl’s nigfltgfow [5,6j _ Witfh the fast three > ears tfwxe hs been o flurry of activity in the spectroscopy of these stales. Caspflase measurements fmve been stimulated by rhe observations of the Russian Venus probes [7j, whicfl in-
[9] and Goodm~u xui Brus Iflat emission from tflc C ‘-1, state if01 (.md from the c ‘X; state) czn bc gencratcd by fasrr e_xcit.!tion of O1 iu rare gtls and nitrogen matrices_ .Iforc recently. tfie xuhr has puhlisltcd ;t prtpcr demonstrating tfls gcncrarion of aff three states (A, C. c) in ;1 helium-o\ygcn dischxgc system [I!] _The trsnsirions new to hboratory gas phase emission sfxcrroscopy were identified, C 3_1, - a ‘1:. C ‘11, -+ x3\---g * 3nd C’Y, -f 3’&, and vibrational conwnts tvcrc obtained :-or the a ‘_& and C 3A, states_ For the st3tcs, only hnsitions originttting c%, and c*x, from tfw u’ = 0 fcveis were found. in accord wit11 tile observations of Lawrence et al_ [S] and tfle Venus spectra [7] _ Over rf~ Past 25 years, uumerous articles flare drscribed unkuown band systems in 07, notabfy tftose first reported by Broids and Caydon [a], and subsequently observed by Bartfl and Kaplan 1 I I] and by Degen et af_ [I 2]_ Furthermore, Degen [IS] 113s pre-
Kichards
sented
* Permaoeot termtioiiai.
addms MoleLxdar Physics Laboratory. WzoIo Park. California 94025. USA_
SRI io-
ad
Jofrnson
1~dw sfunrn
3 rotationllffy
rcsofved
spectrum
of one
of time
bands. Since
in tfie author’s
earlier
paper
[2]
the
C 3Au +
vxiarion tions.
Ior the lercls
t\\crdges
were
obt.xiued
t&xl
from
setvera
transi-
for LB’= 2. ?i_ 4. .tttd utilixd
wti: the Iltr~berg data [l-l] for u = 5 3nd 6 to .I function inlolcing tlwze vIbr.honrtI con%uIts. Tl~e resulkmr consl3ufs xe G,, = S 11 cm-‘. were = 9-6 cm- ’ _ and ~+_t ~ = -0.79 cm-l _snd yield the term v.dues presented in tabIe I_ The d&~erences are small. considering the errors in measuring from the published spectra_ The xhe caIcul.md for Too of34 235 cm -1 (table I ) otsy be conwxed with the v&e of34 2 13 cn- 1 reported earlier (21. Such 3 diiference is es.11ong
obt.tiu
From
the spectr&
presental
by Degeu
et A. [I?]. the v,,wArr?gtIl ol‘exh b.md \\.ts obt.ked by caefuily f mt.mxing Il.s dist.mce froin the nearest X ‘Yu s ;-,-_,, bmd Iiwd. noting tiw the distmce from the kilow11 .\--x=I,e.ld (the @I& liuc) to the sccimtely ori+
is .S_5 cm -I
proposed = 503.5
set of cIn-1_
CC& Ion
U’ [3]_
C 'lu ~hrrttion~l We-Ye
= s.
1s
cm--I
Upon
using the
constants _ wore
[3] (0, =
-0
s77
c.&uLting 3 Deslmdrcs table for the it ~3s evident tht a11 C G,,(fl ! - .i ‘+ rrrtnsitiou. fcu hds of Degm et 4. [ 121 could be n~.mAml. \\itft 3 positiw deviation of5 I 1 X, to give 3 dlstribution folloriing 4 re.wm.hIe Fr.inck-Condou pa-ribofa. Since the \Ibratioml cousfmts hd been obtained in 3n unortI~od0.x ni;Lnner_ due to the psucit> ofavnrlable intbrmation. it was not unrr\pcctcd th3t Sony adjustmeut might be necess.wy_ The bmds seemed to involve transitIons from the U’ = I-4 Ierels of fix C 3+, state. making possible 3 Iink v;itlr he u’ = 5. 6 LVCIS, measured in absorption by 1 lerzberg [I-?] for the upper two spin components of u’ = 6 and the upper component only for u’ = 5. By .tssuming that the splitting of 146 cm-l observed in u’ = 6 is the s.me for the two lower components and for 311 u’, 3s obserwd in the mdtris measurements of Goodnt3n 3nd Brus [IO] _ an accurate niexure of the energy of the F1 component of ZJ’= 5 and 6 is then sv3ilable_ Previously [2] _ it was shown th3t it is only the F1 component that radi3tes in the C 311, + a l-1,? transition. 3n obserwtion borne out by dirglow ob- J sermtions of this system [5] _ The transition ener$es of the ten bands observed by Degeu et al_ [ 121 were then cdcuhted. and the appropriate 3’+ energy added 121; the tot31 excitation energy for e3ch u’ is given in table 1, showing the cm-’
) md
pccted. since the earher data xere based on the band pe.k intensities. noI on the bmd heads 3s measured
from the tirtta of Degen et 31. [ I?]_ The resolution of the previous spectra WJS about 6 =i_ which h3s the effect of shifting the peak baud intensity away from the b_uxi head. By applying a tri.mgular slit f-unction to rfrc resolved band shown in Degen-s prtper [ 131, which is the 4-3 bmd (‘slthough the 1-2 bald has ewctly tile smne band Ilead position). one miy show that the peak intensity is shifted from the IleAd by 3pproxiniJtely 12 crrF* _This is just the dlffereuce between the ;Iboxe values of TOO_ There is thus consistency between the O--v” transition energies from the earlier pspcr [3] _ rhe u’ = 5 md 6 levels measured l-able 1 C 3+(1--t ) cncrg ____I__-___~----
Vibmiom! heI
levels
-
Vibmtional
Deduced
Calcukted
band
energ level (WI-~ 1
energy lexef (cm-’ )
__------__~
34 225
u=O u= 1
1-4
35016
35015
lJ=2
7-3 z-4 z-5
3.5 787 35 782 35 780
3.5 779
ZJ=3
3-Z
36518
36511
3-3 3-4
36511
3-5 u=4
36 507 36 507
-5-z
37 208
4-3
37209
37209
tJ=5
37866a)
u=6
384773
a)Deduced from Herzberg [14]. 34.5
Table 3 Deslandr~~~table for C ‘au(F, ) - 3 ‘A= hands ai -z_. _ _ _.- _- - - .-_____---_ ._^______ J r; = 0 v1 ” =1 d =3 u- = 1 _. ___-_____ -_ __ __--__ _.__^-. -- ---- ^-- --.------. 0 26343b) 24860 23403 I 21973 10 570
3795-O =) 1 2 3
27133 3663.4
4021.4
4271.8 _ 24193
2.5650 3S97J
4 132.2 I
27897 3583.6
26414 249.57 3781.8 4005_s --28630 f-27117 i 25690 3491.8 : 36836 E 35915
f
;
t
1 5 6
29327 34088
! 27S44 i 3590-4
29981 r 28531 3334.2 i 3507.6 i 30595 t ?9I?.Z 3267-6 i 34340 -------_--
i
1549.7
* : 12763 4391-9
31360 46S0.3
i I
I
26 225 3812-2 -_-_
_
_
_
u- = 8
-___---
-
____
lJ” = 9
_-_--------
-
___.
13954 f 7 161.-t - - _14 744 6 780.5
19397
I8074 5 531.3
16 778 5958.6
15 508 6436.5
21480 * 20130 4 654.2 i 4 966.3
I8 807 5 315.8
I7511 5 709.1
16 Z-II 6 155.6
10 837 4 800.2
1950-t 5 125.8
18 208 5 490.6
I6938 5 902.3
71484 4 653.3
20 161 4 958.7
18865 5 399.4
17 595 5 681.8
22 095 4 524.6
20 i-72 4 SE.9
19476 5 133.1
18 206 5 491-z
f1 23554 -s2-t-Z-4 ;1 El77 4 507.9 Z4471l 4 179.3 *----24 822 f 4 027.6
-
7
_ _I5114 6 566.7 5208.8 56022_ A-6051.6 _---19983 /IS&3 x-3lO 16014 5002;9 ’ _- 5365-4 5 775.4 6 242.8 - --- t
22 857 4373.8
,25 614 / 3903.1
_
““Z
I6 520
24 260 4 120.9/ ’
27 043 3696-7
__- - _- _-_ - _____ _-_-
= 6
17 s43
19 193
4960.1 f ji
d
-_--z7=--zYz-F
?2 124 ,20-747 _ _ 4518-7 y 4818.7
24 4005-S 957’
/
L.- = =j
t3 527 -I 219.2
16 3 387 788.6
27655 , 3 615.0
- ______-_ .~__ - _-
: 1-3834 f 4 378.2 23 445 4264.1
;
1
5 154.0
a) The solid line outlines the bands in the spectra of Dcgen et SL [ l21. the dotted line at high U’ shows the ndditionxl bands seen in the nightglo~v 15.61. the dotted Linest low ID’shoxis theadditiona1 bands seen by Shnga [ 2I_ The mr;lboh indimtes the locus of points for maximum qu3 product, using calcuhtions of Aibritton for the A 3X‘;; - ;I ‘4 bands [ l91_ b) Transition ener,p
\‘011u11c 66. nl:Inher
< III
2
VI<
1 October
.\L 1’111SIC 5 I.1 i-1 LIZS
I979
tdcnrrtiwtion
Tfie r‘k.tiiri~tc~f Fr.uiA -Con&m fLktors [IL>] fxw r&2 .I ~ii:cmgcr .irgrrriwt The 1007 -\ fmid, 11‘ it f,~fc>ngcrf t<> rfw X- ;I qstan, \iokf fx tile I-’ bad. .~mf hOUILf be cfuite lie&. >et it is the strongest nonI.\--_\\) Iund m tfie spectra 0P Degen er .[I_ [ 131 _01~ tflc orfm fmxf_ tfie 3-5 -1-d bmd dt 4503 X has .i fxgc fknch--Condon t;lctor snd the X ‘XI; (u = 3) f~c~pul~tton is substantial_ >tt there is no indic3tion of tfw f>ai~f in Ikgcn‘s high resofurion speLtrum of this rcy.m 1I;\_ f%l.!ff> . the .\--a I -3 bud 11~s a kJfue
ftrr B” - IS’ ot 0.496 cm-- I. constdaabf~ 1663
-__
---_-
l-4
less tftm tfut
li)und b&w fix tfie 1007 X bald. Tile discfl~rge data dewonstr~~e tflJt tflC state_ wflicll we fi~ve estim.tted 121 to hare ftfetinte
it’ S--50
s_ sfs~ must be ~try
C ‘A,, J
resisr.mr
r.kfLtive co wbm-
~IWIJI
rei~~~riun. i’rcssures sc\cwf Turr oxygen aerr‘
[ ITI_ It 11s Ilrlm hem shr>\vn [ 161 tht the c-4 band:, drc Lfisccrriiblc in tfic Venus spcctrd .ts we11 I?] _ l’rc~rrn~sly [2]. tmidentificd b.mds nere noted a X95. -fOSO. .md 5002 _-i_ Addition of 13 cm-’ to the transition .‘ncrsies pkes the bald flwds at -G93_ 4677. md 4999 3. compared to c.iIcuIatcd values dl392. -ZGSO_and 5003 A for tfte I-3. I-4. am1 I -SK-4 bmds. 1 his identdkxtion is prob.kbIy correct_ dltfuwpfl the JeviAions for the Litter two bakfs xc some~if~~t greater rfkm for any of those listed in tJbIc 2. On this basis. it is evident tfl& the I-6 C- ;Lb.mJ also appears on the original spectrum. altfmugh poorly resolved. Wraigftt [! 71 flas suggested tfw the bands not identified as _A--?< in the nightglow couId bekmg to the A ‘Xt - ;Ll 1” sysvstem_ Upon Llifculating the pertinent wrtvefengtfG for A j_‘i (u’ = 4, 5, 6). the levels with gratest population in the airgfow [ IS] ~ the best matches to the observed airglow wavelengths listed in tabfe -I show a~crage deviations of 7 A, comp.tred to 2 X for the C-a identifications. Conversely_ the discflarge system bands fisted in
up to 40 Torr argon and used by Degen et 31. [ I2 1 end 8loidJ end G~qdon [-t] _ BroidJ and Gqdon obr.ActI rxiirtticm frrxn levels up w u’ = 5. comparribfe to that seen in the A%: state. v,Iiicli liss d radiatne IXetmie approGmateI> two orders of mztgnitude sflortrr. Thus. only tfle cl\-; state emission 1~s yer to be seen from levels abole u’ = 0 in the gas phase. Tllis .maI> SIS hss identified ~11 rfle bands reported I; Depm et a!_ [I ?I_ aid ~11 cscept wo of tfiose reported by Broida and Gaydon [-tj_ In rhe work of Barr11 and Lpfm [I I] rfzere are Sri11 several unidenrilkf biitxfs. and at Icast fottr of rItetn lend tImiselves to identification .x C 3Au(F2) -+ X km bands. There 2 is no obvious reJ.son wfly tfley should not be present in rtff the systems. Tflere sre even some weak bands in the nightgIow spectrum [5] which seem to be best identified as C-X transitions. The rorationaffy resolved spectrum published by
Dcgen [ 131 cm be pxtially tiona!
const.mts_
tflat the feature band, a conchsion
of the Frmck-Condon _4Itflough
malgzed
to obtain
rota
making it possible to demonstrare is the 4-3 band, rather than the 2-2
there
already suggested by the position locus in table 3.
are features
in the spectrum
that 347
\‘c~!um~66 . flun1bcr1
<.ti1 Mli .\I. 1’111SK s LI-ITI RS
It is ckrr fr01u lkgen's spectrum of the -I007 X band tfw the emission comes onf_v from t11e C ‘l,(F1 ) level_ The band head is at -2006~1007 x. and the P, R branch can be followed distinctiy 3s far as -Kl70 _A, i-e_ more than 60 A_ if the ne_st spin component (146 cm-’ higher) were radiating. its head would be at 39%) _A,and the P and R brrtnches (now separated) wouId extend to at Ieast 4044 A_ Degeni spectrum [ 131 shows no significant emission between 1 set of -4-X lines zi 3999 A snd the 4007 A head, so C3_1,(F2) - ~~1~ emission is absent_ It has been poked out by Krupenie [I 1. rend brought to the athor’s attention by Wraight [12 j? that the C ‘1, state is inverted? so that the Q = 3 csomponent Iia lowest, z point not noted in Mazbeg’s pper on C-X absorption [ 14J_ The mechanism by which C3A (2 = 3). and this component aIone, radiates to a? AgY is not evident. and it is to be hoped that hi& resolution spectra of these bands will shed scme iight on the cause of this unusuai effect.
3. ConcIusiotls The C3% + a1Ag bands of 0, seem to be a common fezlture of 0, aftergIows_ T&y are cert3inIy 318
t OLtober
1979
werthcr thtln the A ‘\-*U - XL--‘g Ixl11c1s_ but as the k&33\+ _u state 1tJ.s2 r.tdktivc lifetime some two orders _ of mrrt;riitirdcshorter than the C’2, state. their concentrations rnxy in fart be cornpar-lbIe_ It is expected that their production rates would be similar in systems sucl~ ;IS zrfterglows and the nightglow. where ,ttotn recombination shou1d be the dominant source. It is .dso evident that \ibr.ttionaI distributions in the two btdtes xc compxabie, both in the laboratory experiments and in the nightglow_ Emission by the third Oz ntstastabIe state in this energy region, c ‘xi * h.ts so far been seen o111y from u' = 0. and therefore appears to be involved in rnucb more rapid V-V or cross rchu.fticn processes_ The spectroscopic constants ewluxted here are suninxtrized in table 5.
Acknowledgement This work was supported by ;Lgrant from the Atmospheric Sciences Section of the ?&tionr?l Science Foundation_
References [I j [3] [3] [4 j
P_H_Kmpenie. J. Phyr Chem_ Ref. Data I (1972) 423_ T-G_ Slarger. J. Chem. Phys_ 69 (1978) 4779_ G. Heberg. Can. J. Phyr 30 (1951) 185. II-P_ Broida and A-G_ Gaydon, Proc. Roy. Sot. A 132 (1954) 181. [.5) A-R. Broadfoot and K-R_ Kendall. J_ Geophys_ Rer 73 (1968) 426s [6] J-P. Hennes. J. Geophys. Res 7I(1966) 76k 171 VA_ KrasnopolWcii. AA_ Rrys’ko. V-N_ Pogshev and V-A- Parshev, Cosmic research. Vol. 13 (Consultants Bureau. New York. 1977) p_ 687_
\‘olume 66. number 2
CflI \IIC.\L PIIYSICS
[SI G.11. L.mrence_ C.1. B.&l and V_ .\rgabright. Science 195 I :%‘7J 573. [91 J-L_ Rich.mls~nd P.U. Johnson. J. Cbxn. PI:)r 65 (1976) 3948. [ 101 J. Goodm.m .md L.L. Brus. J. Chem. 1’11)s. 67 (1977) 1182. [ 111 CA. ILuth axI J. K.1p1.m. J. Mol. Spectr> _3 (1959) 583_ [I? j V_ Dczt?n, S.If_ Inn_men_ G-R. Ilrbert xnd R-K’_ Nicholls, Idsntifution .Was of \lolcculx Spectra. Pxt 6_ The 02 fA 3~t -- N ‘Z,L) Ilerzbrrg I System. Yorh Unnersit) _Toronk. Ont&. Canada ( 1968). [I;] V. DwxI,C-an. J. I’h)s.~6 (1968) 783.
LLl-l LRS
1 October
1979
[IAl C. Ilerrberg, Can. J. Ph)s. 31 (1953) 657. [IS] J-L\‘_C!wnberllnin. Az.roph>~. J. 128 (1958) 713. [ 161 T.G. Sianger and G. BLck, Ccophys. Res. Letters 5 (1978) 917. [ 171 PK. Wr&hr, Xature 163 (1976) 310. [ 181 V_ Degen, J. Gcoph)s. Res. 74 (1969) 5145. [ISi D.A. Xbritton, prir&te communication (197s). [WI C_ Ita-zberg, Spectra of diarornic moIecules, Znci Ed. (Van Nostrand. Princeton, 1950). [?I J L_ Ilerzberg rend C. FIerzberg. Astrophys. J. 105 (1947) 353. [221 P C. \Vraight. private communication (1979).
319
_
staw
cItoms
md
I) ir1g lxtw3m
4 mlf
5 CL’
abotc ihc ground skew. dcsQn;rrcd c’X, _ C 31u. and .\‘Xz_ Tlicsc st3tes_ fikc tfw two fokcr :uet.tstzhfes_ a11 andb “5. do net to 3 first ;Ipprosimarion interact Zill* tic11 Afwr or tits S ‘_‘z ground stitfc, and thus transitions bct\\ecn thcsc s% sf3tcs imolvc radirttive fiktimes in tfw rsnge of fO-1IO-’ s [ 1 .?I_ It is for tfds rcason fht progress Ims been sforv botfl in the spcutrosclopy of the tmnsitions and in tile kinetics of the individual states_ Afthough tile A 3XE + _X3X, trmsition has been known for many years in borh ab sorption [3J and emission [3J. not even for tflis systern are adccfuatc kinetic data for tflc upper sf;ltc zlvzilrtbk, zdtflougfl tfle transition is ofparticuhr importance in the cartfl’s nigfltgfow [5,6j _ Witfh the fast three > ears tfwxe hs been o flurry of activity in the spectroscopy of these stales. Caspflase measurements fmve been stimulated by rhe observations of the Russian Venus probes [7j, whicfl in-
[9] and Goodm~u xui Brus Iflat emission from tflc C ‘-1, state if01 (.md from the c ‘X; state) czn bc gencratcd by fasrr e_xcit.!tion of O1 iu rare gtls and nitrogen matrices_ .Iforc recently. tfie xuhr has puhlisltcd ;t prtpcr demonstrating tfls gcncrarion of aff three states (A, C. c) in ;1 helium-o\ygcn dischxgc system [I!] _The trsnsirions new to hboratory gas phase emission sfxcrroscopy were identified, C 3_1, - a ‘1:. C ‘11, -+ x3\---g * 3nd C’Y, -f 3’&, and vibrational conwnts tvcrc obtained :-or the a ‘_& and C 3A, states_ For the st3tcs, only hnsitions originttting c%, and c*x, from tfw u’ = 0 fcveis were found. in accord wit11 tile observations of Lawrence et al_ [S] and tfle Venus spectra [7] _ Over rf~ Past 25 years, uumerous articles flare drscribed unkuown band systems in 07, notabfy tftose first reported by Broids and Caydon [a], and subsequently observed by Bartfl and Kaplan 1 I I] and by Degen et af_ [I 2]_ Furthermore, Degen [IS] 113s pre-
Kichards
sented
* Permaoeot termtioiiai.
addms MoleLxdar Physics Laboratory. WzoIo Park. California 94025. USA_
SRI io-
ad
Jofrnson
1~dw sfunrn
3 rotationllffy
rcsofved
spectrum
of one
of time
bands. Since
in tfie author’s
earlier
paper
[2]
the
C 3Au +
vxiarion tions.
Ior the lercls
t\\crdges
were
obt.xiued
t&xl
from
setvera
transi-
for LB’= 2. ?i_ 4. .tttd utilixd
wti: the Iltr~berg data [l-l] for u = 5 3nd 6 to .I function inlolcing tlwze vIbr.honrtI con%uIts. Tl~e resulkmr consl3ufs xe G,, = S 11 cm-‘. were = 9-6 cm- ’ _ and ~+_t ~ = -0.79 cm-l _snd yield the term v.dues presented in tabIe I_ The d&~erences are small. considering the errors in measuring from the published spectra_ The xhe caIcul.md for Too of34 235 cm -1 (table I ) otsy be conwxed with the v&e of34 2 13 cn- 1 reported earlier (21. Such 3 diiference is es.11ong
obt.tiu
From
the spectr&
presental
by Degeu
et A. [I?]. the v,,wArr?gtIl ol‘exh b.md \\.ts obt.ked by caefuily f mt.mxing Il.s dist.mce froin the nearest X ‘Yu s ;-,-_,, bmd Iiwd. noting tiw the distmce from the kilow11 .\--x=I,e.ld (the @I& liuc) to the sccimtely ori+
is .S_5 cm -I
proposed = 503.5
set of cIn-1_
CC& Ion
U’ [3]_
C 'lu ~hrrttion~l We-Ye
= s.
1s
cm--I
Upon
using the
constants _ wore
[3] (0, =
-0
s77
c.&uLting 3 Deslmdrcs table for the it ~3s evident tht a11 C G,,(fl ! - .i ‘+ rrrtnsitiou. fcu hds of Degm et 4. [ 121 could be n~.mAml. \\itft 3 positiw deviation of5 I 1 X, to give 3 dlstribution folloriing 4 re.wm.hIe Fr.inck-Condou pa-ribofa. Since the \Ibratioml cousfmts hd been obtained in 3n unortI~od0.x ni;Lnner_ due to the psucit> ofavnrlable intbrmation. it was not unrr\pcctcd th3t Sony adjustmeut might be necess.wy_ The bmds seemed to involve transitIons from the U’ = I-4 Ierels of fix C 3+, state. making possible 3 Iink v;itlr he u’ = 5. 6 LVCIS, measured in absorption by 1 lerzberg [I-?] for the upper two spin components of u’ = 6 and the upper component only for u’ = 5. By .tssuming that the splitting of 146 cm-l observed in u’ = 6 is the s.me for the two lower components and for 311 u’, 3s obserwd in the mdtris measurements of Goodnt3n 3nd Brus [IO] _ an accurate niexure of the energy of the F1 component of ZJ’= 5 and 6 is then sv3ilable_ Previously [2] _ it was shown th3t it is only the F1 component that radi3tes in the C 311, + a l-1,? transition. 3n obserwtion borne out by dirglow ob- J sermtions of this system [5] _ The transition ener$es of the ten bands observed by Degeu et al_ [ 121 were then cdcuhted. and the appropriate 3’+ energy added 121; the tot31 excitation energy for e3ch u’ is given in table 1, showing the cm-’
) md
pccted. since the earher data xere based on the band pe.k intensities. noI on the bmd heads 3s measured
from the tirtta of Degen et 31. [ I?]_ The resolution of the previous spectra WJS about 6 =i_ which h3s the effect of shifting the peak baud intensity away from the b_uxi head. By applying a tri.mgular slit f-unction to rfrc resolved band shown in Degen-s prtper [ 131, which is the 4-3 bmd (‘slthough the 1-2 bald has ewctly tile smne band Ilead position). one miy show that the peak intensity is shifted from the IleAd by 3pproxiniJtely 12 crrF* _This is just the dlffereuce between the ;Iboxe values of TOO_ There is thus consistency between the O--v” transition energies from the earlier pspcr [3] _ rhe u’ = 5 md 6 levels measured l-able 1 C 3+(1--t ) cncrg ____I__-___~----
Vibmiom! heI
levels
-
Vibmtional
Deduced
Calcukted
band
energ level (WI-~ 1
energy lexef (cm-’ )
__------__~
34 225
u=O u= 1
1-4
35016
35015
lJ=2
7-3 z-4 z-5
3.5 787 35 782 35 780
3.5 779
ZJ=3
3-Z
36518
36511
3-3 3-4
36511
3-5 u=4
36 507 36 507
-5-z
37 208
4-3
37209
37209
tJ=5
37866a)
u=6
384773
a)Deduced from Herzberg [14]. 34.5
Table 3 Deslandr~~~table for C ‘au(F, ) - 3 ‘A= hands ai -z_. _ _ _.- _- - - .-_____---_ ._^______ J r; = 0 v1 ” =1 d =3 u- = 1 _. ___-_____ -_ __ __--__ _.__^-. -- ---- ^-- --.------. 0 26343b) 24860 23403 I 21973 10 570
3795-O =) 1 2 3
27133 3663.4
4021.4
4271.8 _ 24193
2.5650 3S97J
4 132.2 I
27897 3583.6
26414 249.57 3781.8 4005_s --28630 f-27117 i 25690 3491.8 : 36836 E 35915
f
;
t
1 5 6
29327 34088
! 27S44 i 3590-4
29981 r 28531 3334.2 i 3507.6 i 30595 t ?9I?.Z 3267-6 i 34340 -------_--
i
1549.7
* : 12763 4391-9
31360 46S0.3
i I
I
26 225 3812-2 -_-_
_
_
_
u- = 8
-___---
-
____
lJ” = 9
_-_--------
-
___.
13954 f 7 161.-t - - _14 744 6 780.5
19397
I8074 5 531.3
16 778 5958.6
15 508 6436.5
21480 * 20130 4 654.2 i 4 966.3
I8 807 5 315.8
I7511 5 709.1
16 Z-II 6 155.6
10 837 4 800.2
1950-t 5 125.8
18 208 5 490.6
I6938 5 902.3
71484 4 653.3
20 161 4 958.7
18865 5 399.4
17 595 5 681.8
22 095 4 524.6
20 i-72 4 SE.9
19476 5 133.1
18 206 5 491-z
f1 23554 -s2-t-Z-4 ;1 El77 4 507.9 Z4471l 4 179.3 *----24 822 f 4 027.6
-
7
_ _I5114 6 566.7 5208.8 56022_ A-6051.6 _---19983 /IS&3 x-3lO 16014 5002;9 ’ _- 5365-4 5 775.4 6 242.8 - --- t
22 857 4373.8
,25 614 / 3903.1
_
““Z
I6 520
24 260 4 120.9/ ’
27 043 3696-7
__- - _- _-_ - _____ _-_-
= 6
17 s43
19 193
4960.1 f ji
d
-_--z7=--zYz-F
?2 124 ,20-747 _ _ 4518-7 y 4818.7
24 4005-S 957’
/
L.- = =j
t3 527 -I 219.2
16 3 387 788.6
27655 , 3 615.0
- ______-_ .~__ - _-
: 1-3834 f 4 378.2 23 445 4264.1
;
1
5 154.0
a) The solid line outlines the bands in the spectra of Dcgen et SL [ l21. the dotted line at high U’ shows the ndditionxl bands seen in the nightglo~v 15.61. the dotted Linest low ID’shoxis theadditiona1 bands seen by Shnga [ 2I_ The mr;lboh indimtes the locus of points for maximum qu3 product, using calcuhtions of Aibritton for the A 3X‘;; - ;I ‘4 bands [ l91_ b) Transition ener,p
\‘011u11c 66. nl:Inher
< III
2
VI<
1 October
.\L 1’111SIC 5 I.1 i-1 LIZS
I979
tdcnrrtiwtion
Tfie r‘k.tiiri~tc~f Fr.uiA -Con&m fLktors [IL>] fxw r&2 .I ~ii:cmgcr .irgrrriwt The 1007 -\ fmid, 11‘ it f,~fc>ngcrf t<> rfw X- ;I qstan, \iokf fx tile I-’ bad. .~mf hOUILf be cfuite lie&. >et it is the strongest nonI.\--_\\) Iund m tfie spectra 0P Degen er .[I_ [ 131 _01~ tflc orfm fmxf_ tfie 3-5 -1-d bmd dt 4503 X has .i fxgc fknch--Condon t;lctor snd the X ‘XI; (u = 3) f~c~pul~tton is substantial_ >tt there is no indic3tion of tfw f>ai~f in Ikgcn‘s high resofurion speLtrum of this rcy.m 1I;\_ f%l.!ff> . the .\--a I -3 bud 11~s a kJfue
ftrr B” - IS’ ot 0.496 cm-- I. constdaabf~ 1663
-__
---_-
l-4
less tftm tfut
li)und b&w fix tfie 1007 X bald. Tile discfl~rge data dewonstr~~e tflJt tflC state_ wflicll we fi~ve estim.tted 121 to hare ftfetinte
it’ S--50
s_ sfs~ must be ~try
C ‘A,, J
resisr.mr
r.kfLtive co wbm-
~IWIJI
rei~~~riun. i’rcssures sc\cwf Turr oxygen aerr‘
[ ITI_ It 11s Ilrlm hem shr>\vn [ 161 tht the c-4 band:, drc Lfisccrriiblc in tfic Venus spcctrd .ts we11 I?] _ l’rc~rrn~sly [2]. tmidentificd b.mds nere noted a X95. -fOSO. .md 5002 _-i_ Addition of 13 cm-’ to the transition .‘ncrsies pkes the bald flwds at -G93_ 4677. md 4999 3. compared to c.iIcuIatcd values dl392. -ZGSO_and 5003 A for tfte I-3. I-4. am1 I -SK-4 bmds. 1 his identdkxtion is prob.kbIy correct_ dltfuwpfl the JeviAions for the Litter two bakfs xc some~if~~t greater rfkm for any of those listed in tJbIc 2. On this basis. it is evident tfl& the I-6 C- ;Lb.mJ also appears on the original spectrum. altfmugh poorly resolved. Wraigftt [! 71 flas suggested tfw the bands not identified as _A--?< in the nightglow couId bekmg to the A ‘Xt - ;Ll 1” sysvstem_ Upon Llifculating the pertinent wrtvefengtfG for A j_‘i (u’ = 4, 5, 6). the levels with gratest population in the airgfow [ IS] ~ the best matches to the observed airglow wavelengths listed in tabfe -I show a~crage deviations of 7 A, comp.tred to 2 X for the C-a identifications. Conversely_ the discflarge system bands fisted in
up to 40 Torr argon and used by Degen et 31. [ I2 1 end 8loidJ end G~qdon [-t] _ BroidJ and Gqdon obr.ActI rxiirtticm frrxn levels up w u’ = 5. comparribfe to that seen in the A%: state. v,Iiicli liss d radiatne IXetmie approGmateI> two orders of mztgnitude sflortrr. Thus. only tfle cl\-; state emission 1~s yer to be seen from levels abole u’ = 0 in the gas phase. Tllis .maI> SIS hss identified ~11 rfle bands reported I; Depm et a!_ [I ?I_ aid ~11 cscept wo of tfiose reported by Broida and Gaydon [-tj_ In rhe work of Barr11 and Lpfm [I I] rfzere are Sri11 several unidenrilkf biitxfs. and at Icast fottr of rItetn lend tImiselves to identification .x C 3Au(F2) -+ X km bands. There 2 is no obvious reJ.son wfly tfley should not be present in rtff the systems. Tflere sre even some weak bands in the nightgIow spectrum [5] which seem to be best identified as C-X transitions. The rorationaffy resolved spectrum published by
Dcgen [ 131 cm be pxtially tiona!
const.mts_
tflat the feature band, a conchsion
of the Frmck-Condon _4Itflough
malgzed
to obtain
rota
making it possible to demonstrare is the 4-3 band, rather than the 2-2
there
already suggested by the position locus in table 3.
are features
in the spectrum
that 347
\‘c~!um~66 . flun1bcr1
<.ti1 Mli .\I. 1’111SK s LI-ITI RS
It is ckrr fr01u lkgen's spectrum of the -I007 X band tfw the emission comes onf_v from t11e C ‘l,(F1 ) level_ The band head is at -2006~1007 x. and the P, R branch can be followed distinctiy 3s far as -Kl70 _A, i-e_ more than 60 A_ if the ne_st spin component (146 cm-’ higher) were radiating. its head would be at 39%) _A,and the P and R brrtnches (now separated) wouId extend to at Ieast 4044 A_ Degeni spectrum [ 131 shows no significant emission between 1 set of -4-X lines zi 3999 A snd the 4007 A head, so C3_1,(F2) - ~~1~ emission is absent_ It has been poked out by Krupenie [I 1. rend brought to the athor’s attention by Wraight [12 j? that the C ‘1, state is inverted? so that the Q = 3 csomponent Iia lowest, z point not noted in Mazbeg’s pper on C-X absorption [ 14J_ The mechanism by which C3A (2 = 3). and this component aIone, radiates to a? AgY is not evident. and it is to be hoped that hi& resolution spectra of these bands will shed scme iight on the cause of this unusuai effect.
3. ConcIusiotls The C3% + a1Ag bands of 0, seem to be a common fezlture of 0, aftergIows_ T&y are cert3inIy 318
t OLtober
1979
werthcr thtln the A ‘\-*U - XL--‘g Ixl11c1s_ but as the k&33\+ _u state 1tJ.s2 r.tdktivc lifetime some two orders _ of mrrt;riitirdcshorter than the C’2, state. their concentrations rnxy in fart be cornpar-lbIe_ It is expected that their production rates would be similar in systems sucl~ ;IS zrfterglows and the nightglow. where ,ttotn recombination shou1d be the dominant source. It is .dso evident that \ibr.ttionaI distributions in the two btdtes xc compxabie, both in the laboratory experiments and in the nightglow_ Emission by the third Oz ntstastabIe state in this energy region, c ‘xi * h.ts so far been seen o111y from u' = 0. and therefore appears to be involved in rnucb more rapid V-V or cross rchu.fticn processes_ The spectroscopic constants ewluxted here are suninxtrized in table 5.
Acknowledgement This work was supported by ;Lgrant from the Atmospheric Sciences Section of the ?&tionr?l Science Foundation_
References [I j [3] [3] [4 j
P_H_Kmpenie. J. Phyr Chem_ Ref. Data I (1972) 423_ T-G_ Slarger. J. Chem. Phys_ 69 (1978) 4779_ G. Heberg. Can. J. Phyr 30 (1951) 185. II-P_ Broida and A-G_ Gaydon, Proc. Roy. Sot. A 132 (1954) 181. [.5) A-R. Broadfoot and K-R_ Kendall. J_ Geophys_ Rer 73 (1968) 426s [6] J-P. Hennes. J. Geophys. Res 7I(1966) 76k 171 VA_ KrasnopolWcii. AA_ Rrys’ko. V-N_ Pogshev and V-A- Parshev, Cosmic research. Vol. 13 (Consultants Bureau. New York. 1977) p_ 687_
\‘olume 66. number 2
CflI \IIC.\L PIIYSICS
[SI G.11. L.mrence_ C.1. B.&l and V_ .\rgabright. Science 195 I :%‘7J 573. [91 J-L_ Rich.mls~nd P.U. Johnson. J. Cbxn. PI:)r 65 (1976) 3948. [ 101 J. Goodm.m .md L.L. Brus. J. Chem. 1’11)s. 67 (1977) 1182. [ 111 CA. ILuth axI J. K.1p1.m. J. Mol. Spectr> _3 (1959) 583_ [I? j V_ Dczt?n, S.If_ Inn_men_ G-R. Ilrbert xnd R-K’_ Nicholls, Idsntifution .Was of \lolcculx Spectra. Pxt 6_ The 02 fA 3~t -- N ‘Z,L) Ilerzbrrg I System. Yorh Unnersit) _Toronk. Ont&. Canada ( 1968). [I;] V. DwxI,C-an. J. I’h)s.~6 (1968) 783.
LLl-l LRS
1 October
1979
[IAl C. Ilerrberg, Can. J. Ph)s. 31 (1953) 657. [IS] J-L\‘_C!wnberllnin. Az.roph>~. J. 128 (1958) 713. [ 161 T.G. Sianger and G. BLck, Ccophys. Res. Letters 5 (1978) 917. [ 171 PK. Wr&hr, Xature 163 (1976) 310. [ 181 V_ Degen, J. Gcoph)s. Res. 74 (1969) 5145. [ISi D.A. Xbritton, prir&te communication (197s). [WI C_ Ita-zberg, Spectra of diarornic moIecules, Znci Ed. (Van Nostrand. Princeton, 1950). [?I J L_ Ilerzberg rend C. FIerzberg. Astrophys. J. 105 (1947) 353. [221 P C. \Vraight. private communication (1979).
319