Rotational-Analysis Of High-Resolution Oxygen Molecule Absorption-Bands In The Region From 1085 To 1165 Angstroms

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Content RO TATIO NAL ANALYSIS OF HIGH-RESOLUTION 0
ABSO RPTIO N BANDS IN THE REGION FROM
1085 to 1165 A
by
H an-chuan L iu Chang
A D is s e r ta tio n P r e s e n te d to the
F A C U L T Y OF THE G RAD UA TE SCHOOL
UNIVERSITY OF SOUTHERN CALIFORNIA
In P a r tia l F u lfillm e n t of the
R eq u irem en t of the D e g r e e
DOCTOR OF PHILOSOPHY
(P h y sic s)
A u gu st 1973
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CHANG, Han-chuan Liu, 1938-
ROTATIONAL ANALYSIS OF HIGH-RESOLUTION
02 ABSORPTION BANDS IN THE REGION FROM
1085 TO 1165 A.
University of Southern California, Ph.D., 1973
Physics, molecular spectroscopy
| University Microfilms, A X ER O X Company, Ann Arbor, Michigan
DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED.
UNIVERSITY O F S O U T H E R N C A L IFO R N IA
THE GRADUATE SCHOOL
UNIVERSITY PARK
LOS ANGELES, CALIFORNIA 9 0 0 0 7
This dissertation, written by
HA N - C H U AN ^ LIU _ C HAN G
under the direction of h§.V.... Dissertation Com
mittee, and approved by all its members, has
been presented to and accepted by The Graduate
School, in partial fulfillment of requirements of
the degree of
D O C T O R OF P H IL O S O P H Y
Dean
DISSERTATION COMMITTEE
->*/ S’ ? , .
31 August, 1973
Internal Technical Report No.: USC-Vac-UV-140
Technical Report
en title d
"RO TATIO NAL ANALYSIS O F HIGH-RESOLUTION Q ?
ABSORPTION BA N DS IN T H E REG IO N F R O M
1085 to 11651"
by
H. C. Chang and M . Ogawa
Submitted by
M . Ogawa, Professor
Department of Physics
University of Southern California
Los Angeles, California 90007
LIST OF F IG U R E S
F ig u r e s
1
2-1
2-2
3
4
5 -a
5-b
6 -a
6-b
7
8
9
10
11
12
13
14
P a g e
0^ A b so rp tio n S p ectru m (1 0 9 5 -1 3 2 0 A ) ..................................... 3
18
0 A b so rp tio n C e ll and D is c h a r g e Tube ..................... 6
L d
0 ^ A b so rp tio n C e ll in L iquid B a t h ..................................... 7
3n - x V at 1162 A ............................................................................. 11
u g
Two T yp es of C r o s s in g of P o te n tia l C u r v e s .................. 15
1 4 * 3 1 1 3
E , E , E & II - X E B an ds in the R eg io n
u u u u g
1 1 5 5-52 A ....................................................................................................... 25
3 e \ 1E+ - X^E B ands at 1148 and 1144 A ............................ 31
u u g
3E +, Jn - X 3E B ands at 1125 A ................................................. 28
u u g
3n , ^E* - X 3E B ands at 1121 and 1120A ............................ 41
u u g
4f C o m p lex - a* H 0 3 A ............................................................ 57
3 - 3 + 3 o
E , E - X £ B ands at 1102 and 1101 A , and
u u g
W eak Bands (a), (b), (c) at 1098 and 1095 A ........................ 72
E n e r g y D ia g r a m of the U pper S tates of the O b served
B a n d s ................................................................................................................. 88
P o te n tia l C u rv e s of 0 by K rupenie (See R e fe r e n c e
1 ) .......................................... 93
3 - 3 -
E - X E T ra n sitio n D ia g r a m . . . . . . ................................... 94
u g
3 3 -
^ 2 ^ 3 ^ " ^ ^ g ^ r a n s *t*on D ia g r a m .......................................... 95
3 3 -
IIjfF^) - X E T r a n sitio n D i a g r a m .......................................... 96
3 3
II o ( F i T r a n s i t i o n D ia g r a m .......................................... 97
ii
LIST O F FIG U R E S - C on tin u ed
F ig u r e s P a g e
3 + 3 -
15 £ - X £ T r a n sitio n D ia g r a m .........................................................98
u g
1 3 -
16 II - X E T ra n sitio n D i a g r a m ........................................................99
u g
1 - 3 -
17 E - X E T ra n sitio n D ia g r a m ..................................................... 100
u g
1 + 3 -
18 E - X E T ra n sitio n D ia g r a m ..................................................... 101
u g
i ii
L IST OF T A B L E S
T a b le
l - a ( F 3 )
! - a ( F 2 )
l - a ( F 1)
1-b
2-a(n+)
2-a(n")
3 -a
3-b
3 - c
4 - a
4 -b
5
6
7
8 - ( F 3 )
s - ( f 2 )
5 - f F j )
(t t 2p)(3pa ) 3n - X 3S " (0-0) Band at 1162 A.
g u g
(t t 2p)(3pa ) 3n - X 3S" (0-0) Band at 1162 A .
g ^ u' g
(t t 2p)(3pcr ) 3n - X 3E “ (0-0) Band at 1162 A.
s ^ s
(t t 2p)(3pa ) 3n - X 3E (1-0) Band at 1136 A
g r u' u g
(rr 2p)(4pa ) X n - x V (0-0) Band at 1152 A
g * u' u g
(ng 2p)(4pau ) X nu - X 3E g
(ng 2 p )(4 p n u ) 3 E* - X 3 E g
(T T g 2 p )(4 PT T u ) V - x V
( T T g 2 P )(4 p n u) V - X 3E g
( T T g 2p)(4pTTu ) V - x V
(T T g 2 p )(4 PT T u ) V - X 3S g
(T T g 2 p )(3 PT T u ) V - X 3E g
(T T g 2 p )(4 p n u ) V - X 3Sg
( V P > ( 4P"U) " X \
(T T g 2 p )(4 p a u ) 3 nu - x V
11 2 1 A ........................................
(T T g 2 p )(4 p a u ) 3nu - X 3S g
1121 A .......................................
(Tig 2 p )(4 p a u ) 3nu - X 3E g
1 1 2 1 A .......................................
0 -0 ) Band at 1152 A. .
0 -0 ) Band at 1148 A . .
1-0) Band at 1125 A. .
2 -0 ) Band at 1101 A. .
0 -0 ) Band at 1144 A • .
1-0) Band at 1120 A . .
6 -0 ) Band at 1155 A . •
0 -0 ) Band at 1154 A . .
0 -0 ) Band at 1153 A . .
0 -0 ) or (1-0) Band at
0 -0 ) or (1-0) Band at
0 -0 ) or (1-0) Band at
P a g e
16
17
18
20
23
24
32
35
36
39
42
44
48
50
52
53
54
IV
LIST O F T A B L E S - C on tin u ed
T a b le P a g e
3
9 - a 4f C o m p lex - X E (0 -0 ) Band at 1106 A ............................ 60
§
3 o
9-b 4f C o m p lex - X E (0-0) Band at 1105 A ............................ 62
&
9 - c 4f C o m p lex - X^E (0-0) Band at 1104 A ........................... 63
&
9 -d 4f C o m p lex - X^E (0 -0 ) Band at 1104 A ........................... 64
s
9 - e 4f C o m p lex - X^E (0-0) Band at 1103 A ........................... 66
9 -f 4f C o m p lex - X 3E" (0-0) Band at 1103 A ........................... 67
s
9 -g 4f C o m p lex - X^E (0 -0 ) Band at 1103 A ........................... 68
§
9 -h 4f C o m p lex - X^E (0-0) Band at 1102 A ........................... 6 9
&
10 (rr 2p)(4prr ) ^E - X^E (1-0) Band at 1102 A ................ 73
g c u u g
1 1 -a W eak B ands fr o m 1095 to 1198 A ........................................... 76
11-b W eak B ands fr o m 1095 to 1198 A ........................................... 77
1 1 -c W eak B ands fr o m 1095 to 1198 A ........................................... 79
12 (t t 2p)(5pCT ) 3II - X 3E" (0-0) Band at 1088 A 81
g ^ n' u g
13 0 A b so rp tio n B ands A n alyzed in the R egion fr o m
C a
1085 to 1165 A ....................................................................................... 84
v
A C K N O W L ED G M EN TS
I w is h to e x p r e s s m y deep gratitude to P r o f e s s o r M a sa ru
Ogawa fo r su g g estin g the p r o b le m and for h is invaluable guidance and
en c o u r a g e m e n t during the c o u r s e of this in v estig a tio n , and to P r o f e s
s o r s G erhard L. W e is s le r and R o b ert A . B eaud et for th eir in te r e s t,
a d v ic e, and r e v ie w of this d is se r ta tio n .
I a m s p e c ia lly indebted to D r. Y. Tanaka and D r. K. Y oshino
of the A ir F o r c e C am b rid ge R e s e a r c h L a b o ra to r ie s for th eir e n
co u r a g e m e n t of this w o rk and for lettin g us u s e their e x c e lle n t high-
r e so lu tio n p la te s .
I a m a ls o gra tefu l to P r o f e s s o r E . M e isc h e r for the in sp irin g
d is c u s s io n about the f c o m p le x e s .
F in a lly , I would lik e to thank m y husband, Y u-W en fo r his
help w ith the d raw in gs and for h is understanding and p a tien ce during
the w h ole p erio d of this w ork.
A B ST R A C T
R otational a n a ly s is has b e e n c a r r ie d out for the f ir s t tim e of
the h ig h -r e s o lu tio n ab sorp tion s p e c tr u m of oxygen m o le c u le in the
w a v elen gth r e g io n fr o m 1085 to 1165 A. A ll the o b se r v ed bands a re
c la s s ifie d as R ydberg bands con vergin g to the ground state of ionic
+ 2
oxygen m o le c u le 0 , X II • M o lecu la r con stan ts a r e obtained and
^ §
e le c tr o n ic s p e c ie s a r e g iv en fo r a ll the upper sta te s of the o b serv ed
band s. M ost of th em a r e due to an e x cita tio n of a (t t 2p) e le c tr o n to
§
the np R yd berg o r b ita ls . A 4f c o m p le x is a ls o o b se r v e d w h ich show s
v e r y unusual rotation al str u c tu r e . A n a ly sis for the 4f c o m p le x w as
c a r r ie d out but not c o m p le ted . In teraction s of stab le R ydberg sta te s
and r e p u lsiv e n o n -R yd b erg s ta te s h ave b een su g g e ste d to account for
so m e of the u n expected r e su lts for R ydberg s ta te s .
T A B L E OF C O N T E N T S
P a g e
LIST OF F I G U R E S ....................................................................................... ii
LIST OF T A B L E S ......................................................................................... iv
A C K N O W L E D G M E N T S ............................................................................ v i
A B S T R A C T ............................................................................................................ v ii
C H A PTER
I. IN T R O D U C T IO N ...................................................................... 1
II. E X P E R IM E N T A L S .............................................................. 5
III. ANALYSIS AND R E S U L T S .............................................. 9
3 3 _
1. (t t 2p)(3pa ) n - X E B ands at 1162
g U U g
and 1136 A ....................................................................... 10
2. (rr 2p)(4pa ) Jn - B ands at 1152
g ^ u' u g
and 1125 A ....................................................................... 21
3. (t t 2p)(4pn ) 3E + - X 3E " B ands at 1148
g u g
and 1125 A ....................................................................... 30
4. (rr 2p)(4prr ) *E+ - X 3E B ands at 1144
g ^ u' u g
and 1120 A ....................................................................... 38
5. (n 2p)(3pn ) *E^" - X 3E (6 -0 ) B ands at
g u' u g
1155 A (a s y s t e m ) ..................................................... 43
3 - 3 -
6. (t t 2p)(3prr ) E - X E (0-0) Band at
1 1 * 5 4 1 . . . " . . " .............* ......................................... 46
7. (t t 2p)(4Pt t ) X E" - X 3e “ (0-0) Band at 1153
g ^ ^ u' u g
A ............................................................................................ 49
v iii
T A B L E OF C O N TEN TS - Continued
P a g e
8. (t t 2p)(4pa ) 3n - x V (1-0) or (0-0)
g c c u u g
Band at 1121 A ............................................................. 51
3 _
9. 4f C o m p lex - X £ (0-0) B ands in the
S
R egion fr o m 1106 to 1103 A .............................. 56
10. (rr 2p)(4pTT ) 3£ - X 3 £ (1-0) Band at
g r u' u g
1102 A ............................................................................... 71
11. W eak B ands fr o m 1098 to 1095 A ........ 75
12. (tt 2p)(5pa ) 3n - X 3S (0-0) Band at
g ^ u' u g
1088 A ............................................................................... 80
IV. SUMM ARY OF R E SU L TS AND CONCLUDING
R E M A R K S ............................................................................... 83
R E F E R E N C E S ............................................................................................... 90
A P P E N D I X ....................................................................................................... 92
ix
C H A P T E R I
INTRODUCTION
M o le c u la r oxygen is one of the m o s t abundant c o n stitu en ts of
the ea rth a tm o sp h e r e . T horough in v e stig a tio n is v e r y m u ch in n eed to
und erstand v a r io u s phen om en a in the upper a tm o sp h e r e a s w e ll a s in
the lo w e r a tm o sp h e r e , su ch a s its d is s o c ia tio n , p r e d iss o c ia tio n , io n
iza tio n and r e co m b in a tio n p r o c e s s e s . It h a s b e e n studied b y m a n y in
v e s tig a to r s . A g r e a t d e a l am ount of s p e c tr o s c o p ic data has b een ob
tained, w h ich w a s r e v ie w e d ju s t r e c e n tly by K ru p en ie. * A cop y of the
p oten tial e n e r g y c u r v e s g iv en by K rupenie is inclu d ed in the A ppendix.
H o w ev er, b e c a u s e of the lack in g the 0 e m is s io n s p e c tr u m and the
c o m p le x ity of the a b so r p tio n s p e c tr u m , v e r y little is known a s to the
e le c tr o n ic s p e c ie s and m o le c u la r co n sta n ts of the upper sta te of the
strong ab so rp tio n bands of 0 in the u ltr a v io le t r eg io n fr o m 1000 to
b
O
2000 A, e x c e p t the Schum ann-R ung s y s t e m and a few of the w ea k bands
4
( s e e R e f e r e n c e s 2 and 3). P r ic e and C o llin s w e r e the f ir s t to r e p o r t
th e ir stu d ie s of the bands in the r e g io n b e tw e e n 650 to 1300 A .
5 o
Tanaka la te r studied bands in the r e g io n fr o m 1000 to 1300 A. P r ic e
4
and C o llin s had in d icated that the bands in the r e g io n of w a v elen gth
g r e a te r than 1000 A w e r e due to e x c ita tio n of 0^ fr o m the ground sta te
3 _
X £ to d ifferen t R yd berg s ta te s (orb its) co n v erg in g to the ground
6
+ 2
state of io n ic 0_, X n . R e c e n t c a lc u la ted r e s u lt s of S ch aeffer and
2 g
1
2
Harris^* sh ow s that th e re is no stab le n on -R yd b erg state in th is r eg io n
that could contribute to any a llow ed tra n sitio n fr o m the ground state of
0 . It is th e r e fo r e b e lie v e d that a ll the strong ab so rp tio n bands in the
re g io n 1000 to 1300 A a r e lik e ly due to tra n sitio n s fr o m ground state
3 _
of 0 , X £ to upper R ydberg s ta te s . To id en tify th e s e s ta te s a s to
2 g
th eir e le c tr o n ic s p e c ie s and m o le c u la r c o n sta n ts, w e have for the
f ir s t tim e , c a r r ie d out h ig h -re so lu tio n v ib r a tio n a l and rotation al a n a l
y s is of the bands in the r e g io n fr o m 1085 to 1165 A, w h er e m o s t of
th em exh ib it ro tation al s tr u c tu r e s . (See F ig u r e 1).
The e n e r g ie s of R yd berg sta te s T in m o le c u le s a r e an alogous
X V .
to that in a to m s. T h ey a r e e x p r e s s ib le as:
T R = Tro - R /(n * )2 (1)
w h er e T is the e n e r g y of the s e r ie s lim it, R , the R ydberg constan t,
00
and n*, the e ffe c tiv e p r in c ip a l quantum num ber w h ich equals to n - ( i .
n is the p r in c ip a l quantum nu m b er and |a, the quantum d efect.
Of m o s t of the a n alyzed R ydberg bands in th is reg io n , the
upper sta te s a r e d e r iv e d fr o m a np e le c tr o n and the c o r e . S in ce the
e le c tr o n ic con figu ration of the ground state is
2 2 2 4 2
K K (a 2s) (a 2s) (a 2p) (t t 2p) (t t 2p) , th e e x c i t a t i o n o f a rr 2p e l e c -
g u g u g g
tron to a np orbit w ill r e s u lt in the follow in g sta te s:
1 3
(t t 2p)(npa ) n , II
g u u u
3
44.6A BAND
I094.2A 5-0
1 1 995A
i 4-0
I I9&5A
I302.2A
F ig u r e 1. 0^ A b so rp tio n Spectrum. (1 0 9 5 -1 3 2 0 A)
4
/ -» w \ - 1 + 3 - 3 + 1 3
(TT_2p)(iip T T ) ------- E , E , E , E , A, A
g 1 7 u u u u u
7
A m ong th e s e , the e le c tr ic dip ole allow ed tra n sitio n s fr o m the ground
3 - 3 - 3
sta te X £ a r e to sta te s E and n , and forbidden tr a n sitio n s to the
g u u
r e s t of the sta te s . T h ere a r e a ls o bands n ea r the sh o r te r w a velen gth
end of the r e g io n of in te r e s t due to tr a n sitio n s to nf c o m p le x fr o m the
ground sta te . F o r nf c o m p le x the s ta te s can on ly b e defined in te r m s
of Hund's coupling c a s e (d), or in te r m e d ia te b e tw e e n c a s e (a) and (d)
or (b) and (d).^
It is n e c e s s a r y to point out h e r e an e x tr e m e im portant and f o r
tunate p r o p e r ty of 0 , the n u c le a r spin of 0^ is z e r o . T his lea d s to
the fa c t that the m o le c u le only p op u lates the s y m m e tr ic rotational
g
l e v e l s . T hus, rotation al lin e s due to tra n sitio n s of a ll the a n tis y m
m e tr ic le v e ls a r e m is s in g , and the s p e c tr u m is c o n sid e r a b ly
sim p lified .
C H A P T E R II
E X P E R IM E N T A L
The 0 6 ab so rp tio n sp e c tr a in the argon continuum r eg io n
w e r e photographed w ith the 6. 5 m e te r sp e c tr o g r a p h at the A ir F o r c e
C am bridge R e s e a r c h L a b o r a to r ie s. O xygen gas w a s flow ed through
the m a in ch am b er of the sp e c tr o g r a p h and its p r e s s u r e w as m ain tain ed
at con stan t in the range of 6 to 150 fj, (path len gth 13 m e t e r s ) . The
s p e c tr a w e r e photographed in the secon d o r d e r , w ith a grating of 1200
l i n e s / m m w h ich r en d ered a d is p e r s io n of 0 .6 5 A /m m ap p ro x im a tely .
In ord er to id en tify the vib ra tio n a l quantum num ber of ea ch
18
band, the iso to p e 0^ ab sorp tion sp e c tr a w e r e photographed w ith our
3 m e te r sp e c tr o g r a p h equipped w ith a ls o a 1200 l i n e s / m m gratin g.
The setup of the e x p e r im e n t is shown in F ig u r e 2-1. B e c a u s e of the
18
s c a r c ity of the iso to p e 0^ , it w a s n e c e s s a r y to e n c lo s e the g a s in the
a b so rp tio n c e ll w h ich w a s held at p r e s s u r e s in the range of 0.1 to 8
m m . U n fortunately w e w e r e not ab le to obtain the sp e c tr a of all the
bands w h ich appear in the 0 ^ p ic tu r e , but only half as m an y bands
w h ich a r e lo ca te d in the lo n g er w a v elen g th sid e of the r e g io n of in te r
e s t.
A t the s a m e tim e , in o r d e r to id en tify the band heads or the
e a r ly m e m b e r s of e a c h branch, the 0 ^ ab sorp tion sp e c tr a at liquid
c *
n itr o g e n tem p e r a tu re w e r e photographed w ith our 3 m e te r s p e c tr o
graph. The setup is shown in F ig u r e 2 -2 w ith the ab so rp tio n c e ll
5
DISCHARGE TUBE FOR LIGHT SOURCE
ARGON 0' + HELIUM ARGON WATER
SPECTROGRAPH
, 1 cm
W I N D O W
Li F WINDOW
ALUMINUM
ELECTRODES
PUMP WATER
ENTRANCE
SLIT
ABSORPTION TUBE
SPARK GAP
3m m
5 0 0 p F
AC 0 — 15 KV
18
F ig u r e 2- 1. 0 A b sorp tion C ell & D isc h a r g e Tube
c *
O '
a r g o n
I
SPECTROGRAPH
A R G O N
H e PUMP
WATER
LIQUID N IT R O G E N W I N D O W
COLD BATH
WATER
ENTRANCE
SLIT
ALUMINUM
ELECTRODES
SPARK GAP
5 0 0 pF
A C 0 - 1 5 KV
F ig u r e 2 -2 . 0^ A b sorp tion C ell in Liquid Bath
flow ed w ith 0 g as and im m e r s e d in the liquid n itr o g e n bath. No
c *
window w a s u sed b etw een the a b sorp tion c e ll and the sp ectrograp h .
C H A P T E R III
ANALYSIS AND R E SU L T S
The a b sorp tion lin e s w e r e m e a s u r e d w ith a co m p a ra to r . The
strong lin e s w e r e m e a s u r e d at le a s t fr o m th r ee d ifferen t p la te s and
w eak o n es at l e a s t fr o m two d ifferen t p la te s . The m e a s u r e m e n ts w e r e
a v e r a g ed for ea c h lin e . A to m ic n itr o g e n lin e s w e r e u se d a s standard
lin e s to ev a lu a te the d is p e r s io n c u r v e s . E d l e n ' s ^ and B o y e r and
R o b in s o n 's ^ w a v e le n g th ta b le s w e r e u se d for the w a v elen g th s of the
standard lin e s .
S ince the ground state ro tation al le v e ls a r e w e ll known fr o m
12
the w o r k of B a b co ck and H erzb erg , the a n a ly s is w a s m a in ly b a se d
on the follow in g com b in ation r e la tio n s:
R(N) - P(N+2) = A9F"(N +1) for R and P b r a n c h e s,
SR(N) - Q(N+2) = A2F"(N+1) for SR and Q b r a n c h e s and
Q(N) - °P (N +2) = A _F"(N -1) fo r Q and ° P b r a n c h e s.
A9F"(N ) is the e n e r g y d iffe r e n c e b e tw e e n the two rotation al le v e ls
C t
(N +l) and ( N - l) of the ground s ta te s , and a r e g iv en b y B a b co ck and
H erzb erg?^
The s c h e m a tic d ia g r a m s of all the tr a n sitio n s o b se r v e d fr o m
3 _
the ground sta te X E a r e g iv en in the appendix.
S
In the ta b le s g iv en follow in g ea c h band d is c u s s io n , the c a lc u
lated v a lu e s (su b scr ip ted cal) for the rotation al lin e s , if g iv en , a r e
10
b a se d on the m o le c u la r con stan ts obtained fr o m the o b se r v e d b r a n c h e s.
T hey a r e only g iv en for bands that have b ra n c h e s w ith enough higher
m e m b e r s to ev a lu a te a c c u r a te enough m o le c u la r c o n sta n ts.
1.. (T T 2p) (3pa )3II - X^E B ands at 1162, and 1136 k :
g c r u u_______ g_________________________________
a . (0-0) Band at 1162 A:
T h is is the f ir s t band at the lo n g er w a v elen g th end of the r e g io n
(1 0 8 5 --1 1 6 5 A), co r re sp o n d in g to group "a" of T a n a k a 'sf The band
w a s c h o se n to be f ir s t a n alyzed , sin c e it appeared to be s im p le s t
am ong a ll the tr ip le t bands o b se r v e d . The p r e lim in a r y r e s u lt has b een
13 3
rep orted . The r e s u lt show s that the upper state is a II state w ith
coupling b etw een H und's c a s e (a) and c a s e (b) but v e r y c lo s e to c a s e
14
(a). A cco rd in g to Budo, th e re a r e to ta lly 24 b ra n c h e s (27 if
3 3 -
including th ree e x tr e m e ly w e a k on es) fo r a n (c a s e a) - E^ tr a n s i
tion. W ith s o m e of th o se a s u n r e s o lv e d s a te llite b r a n c h e s, w e have
a ctu a lly o b se r v e d a total of 15 b r a n c h e s, fiv e for ea ch sp in state. The
sp e c tr u m and the a s s ig n m e n t of the b ra n c h e s a r e shown in F ig u r e 3.
T he l is t of the b r a n c h e s o b se r v e d and the e ffe c tiv e rotational con stan ts
and band o r ig in s , defined a s the e n e r g y of ea c h spin state at J = 0 (as
v ir tu a l sta te s for F^ and F^ sta te s) m e a s u r e d fr o m the F^ le v e l of the
N = 0 (J" = 0 le v e l) of the ground sta te , a r e g iv en in T a b les l-a ( F g ) ,
l-a fF ^ ), and l-a (F ^ ).
O a . 3 n u- X 3I g ( I I 62 A )
„ 23 I
R, i n n 11 i ' t t i i
Q.
rR 23
31 1 ' 1
I 3 21
i 7" t i i i i i r~i— i — i —t—i— i-------1 i
s Q 25 ° 32 I 3 19
'3 2
mii ii1111 ii i i n 1111 ii P
r 3 2
i i i i i i i— i i i--------1 — r
I 31
rm-n i i— i —i — i — i — > — i—
H n n m I i ‘T" I
27
°p
M2
PQ|2
! i - > -1 t\
III*? 11*
f * i ■ v •
n u i i j i j i
r7Hl{!
, i f n n r w !
i ji TV 5 -Hi
I I h ! tit..
T \ -r- 1 . .
v.M -iu-
: C *
" 0 a n n u m 1 1 1 ' i i
Wzi 2 5 q 1^3____ 21
* R — III i-i.l I _______I --------- 1 U ____________
21 2 7 I 3
PQ
23
_ i I I I l_
27
23
F ig u r e 3. ^ 11 - X £ at 1162 A
u g
12
Slight d iffe r e n c e in the m o le c u la r co n sta n ts is o b se r v e d in the
3 - 3 +
n Q and n Q s ta te s , in d icatin g a X -type doubling. T h is is not ob-
3 3
s e r v e d in the n _ and n s ta te s , b e c a u s e the am ount of sp littin g s in
b 1
3 15
the th ree spin sta te s of II a r e d ifferen t for X-type doubling. The
la tte r two spin sta te s h as r e la t iv e ly s m a lle r sp littin g s, w h ich are
n e g lig ib le in the c a s e h e r e .
It h as b e e n conclu ded that this is a n o r m a l (vs in verted ) tr ip le t
state by exam in in g the shading of so m e of the u n r e so lv e d lin e s . U sing
14 i
B u d o's equations for the r e la tiv e in te n s itie s and Y = (A /B ^ )« (9 1 /1 . 4)
= 65, w h er e A is the spin coupling con stan t, w h ich is the d iffe r e n c e
b e tw e e n the spin sta te s F^ and F ^, or F j and F^, one has ca lcu la ted
the in te n s itie s of all the 24 b r a n c h e s. To d e ter m in e w h eth er the
h ig h e st spin sta te is F^ (norm al) or F^ (in verted ), one n o tes that for
s s
F^ a s the upper sta te , the u n r e so lv e d b ra n ch (es) ■ ^ ■ 3 2 '* ' Q3 1 *s c o r r e -
sponding to that of Q .+ ^ R 1 9 for F ( s e e A ppendix). N a m e ly , for ea ch
X l u X
b ran ch lin e (s) the d iffe r e n c e b etw een the J valu e of the upper ro ta tio n
al le v e l and N v a lu e of the ground state rotation al le v e l is one, for
both of the b r a n c h e s of F^ and F ^ . The c a lc u la ted in te n s itie s show
s s
that R ^ f N ) > Q gj(N ), su g g e stin g that the u n r e so lv e d b ra n ch (es)
s s
R 3 2 + should b e shading to the sh o r te r w a v elen g th sid e, sin c e
F ”(N) - F y (N )« F £ (N ) - F ^ ( N ) « 2 c m - 1 (excep t for N = 1). At the sa m e
tim e , Q j(N ) > ^ R ^ N ) s u g g e s ts that b ra n ch (es) s ^ou^
shading tow ard the lo n g er w a v elen g th s id e . C lo s e exam in ation sh ow s
13
the the lin e s of the b ra n ch (es) in q u estion in the h ig h e st spin subband
is shading to the sh o r te r w a v elen g th sid e . T h e r e fo r e , it is conclu ded
3
that this is a n o r m a l n sta te.
u
18
The iso to p e 0^ ab so rp tio n sp e c tr u m photographed w ith our
own sp e c tr o g r a p h sh ow s no sh ift of th is band. The v ib ra tio n a l quan
tum num ber v' of this state is th e r e fo r e z e r o . The n* valu e c a lc u
lated using e x p r e s s io n (1) w ith T ( = 97365 c m * ) ^ being the s e r ie s
00
lim it of the v' = 0 s e r i e s , y ield s a v a lu e of 3. 11. T his value is too
big for a 3p e le c tr o n a s one h as e x p ected fo r this state.
T h ere a r e two c h a r a c te r is t ic s of th is band: (1) the rotational
-1 3
constan t B 1 (= 1 .3 9 8 c m , e ffe c tiv e rotation al con stan t of the n spin
v 1
state) is too s m a ll fo r a R yd b ergb an d co n v erg in g to the ground sta te of
0*, and (2) the e ffe c tiv e p rin cip a l quantum nu m b er n* (=3.11) is too big a s
m en tion ed ab ove. To exp lain the s m a lln e s s of B one n otes that the
v
rotation al con stan t B 1 of X^n of 0^ is 1. 679 c m The R ydberg
v g 2
s ta te s should all have the ro tation al c o n sta n ts fa ir ly c lo s e to th eir
s e r i e s lim it. H ow ever, B 1 of th is band is only 1. 398 c m \
v
It h as b een s u g g e ste d that th e se p e c u lia r r e s u lt s a r e due to the
3 6
in te r a c tio n of a stab le R ydberg s ta te s and a r e p u lsiv e state ( n^II)
w h ich d is s o c ia te s into two n o r m a l a to m s . T h e s e two sta te s happen to
c r o s s each other at the outer lim b of the sta b le state around the in te r -
n u c le a r d ista n c e r^wl. 22 A (“ 1 / ^ I P ) . The in te r a c tio n is strong enough
that the n o n -c r o s s in g ru le a p p lie s. A new sta te is fo rm e d w ith higher
e n e r g y and la r g e r in te r n u c le a r d ista n c e (F ig u re 4 - a ). T h is ex p la in s
s a tis fa c t o r ily the ir r e g u la r it ie s of B 1 and n*. A t the sa m e tim e , the
strong and d iffu se ab so rp tio n b an d s, the " lo n g e st band" (1244 A), the
o o 5
" seco n d band" (1206 A), and the "third band" (1172 A) at the lon ger
w a v e le n g th sid e a r e lik e ly due to the sh a llo w upper sta te fo r m e d by
the r e s t p a rt of the above two state a s show n in F ig u r e 4 - a , w ith the
" lo n g est band" bein g the v' = 0 m e m b e r , and the " secon d band*™ the
v' = 1 , and the "third band," the v' = 2 of the p r o g r e s s io n .
f i g u r e 4
^ T y p e s o r C r
0 8 S‘n g “^ o tentia
c u rVe
TABLE 1 - a(F )
(rr 2p)(3pcj ) IL
g u t
x 3 e ” (0-0) Band at 1162 A
SR32<+ S q >31
Q3(+Q
P 32J
T r
31
F
Obs Cal Obs Cal Obs Cal Obs
1 A 8 6 0 9 0 .7 86101.1 86101.3
3 8 6 0 9 6 . 6 9 6 .4 + 8 6 0 7 8 .4 8 6 0 7 8 .4 1 1 2 .7 112. 7 * 8 6 0 7 2 .9
5 A 1 0 2 . 1
7 2 .9
7 2 .5 124. 0 124. 1 * 6 1 .1
7 107.3 1 0 7 .7 A 6 6 . 7 135. 5 135.5 A
9 1 1 2 .7 113. 3
A
6 0 . 8 147.5 146. 7 * 3 7 .5
1 1 118.6 118. 7 5 5 .4 54. 9 1 5 8 .6
1 5 7 .9 * 2 6 .6
13 124. 0 1 2 4 .2
A 48. 9 1 6 9 . 6 169. 0 * 14.6
15
129.9 129.5 4 3 .4
4 2 .9
1 8 0 .2 180. 0
17 135.5 1 3 4 .7 3 7 .5 36. 8
191. 1 1 9 0 .9
< - °
II II
19
2 1
13 9.6
1 4 4 .4
1 3 9 .9
144.6
A
3 0 .5 2 0 1 .4
2 1 1 .9
201. 5
2 1 2 . 0
23 149.3 149.3 D 1 =
25 1 5 4 .4 153. 8
V
27 15 8.6 158. 1
Cal
86072. 6
61. 1
4 9 .5
3 7 .9
2 6 .3
14. 6
R 3+ R p 31+R° 3 2
Not
R e so lv a b le
- 1
" ( ■ A ll the rotational a ssig n m e n ts a r e given in the w avenum ber unit (cm ) in the T ab les 1 through 12.
A P o sitio n of lin e c o v e re d by w ide ab sorp tion , not a c c u r a te ly m e a su r a b le .
4 P o sitio n e stim a te d by ^F*3 2 > sin c e in te n sity of ^ P 3 2 (N )< Q3 (N) for N < 5 but ^ P 3 2 (N )> > Q3 (N)
o th e r w ise .
( ) Sam e as A , but p o sition of lin e e stim a te d by com bination relation .
* B lended lin e
TA BLE 1 - a(F )
( t t 2p)(3pcr ) 3 n . - X 3 e" (0-0) Band at 1162 A
r q
u
(+R2 )
P Q
23
(+p 2 )
SR
2 1 ° P 23
N
1
Obs
8 6 0 0 0 .7
Cal
8 6 0 0 0 . 1
Obs Cal Obs
8 6 0 0 8 .4
Cal
860 0 8 .5
Obs C al
3 5 .3 5 .3 859 8 5 .6 8 5 9 8 5 .7
* 19. 1 19.3 8 5 9 7 9 .6 859 8 0 .1
5 A 1 0 . 2 9 7 9 .6 9 7 9 .4 * 2 9 . 8 29. 7 9 6 8 . 8 9 6 8 . 2
7 * 14.6 1 4 .2
A 972. 8 4 0 .5
3 9 .9 956. 6 9 5 6 .0
9 * 19.1 19. 0 9 6 5 .3
9 6 5 .9 50. 5 49. 7 A 9 4 3 .5
1 1 23. 6 2 2 . 9 9 5 9 .2 9 5 8 .6 A 59. 1 9 3 1 .0 9 3 0 .7
13 ¥ 2 6 .6 2 6 .4 950. 8 9 5 1 .0 6 8 .5 6 8 . 3 A 9 1 7 .5
15
* 29. 8 2 9 .6 A 9 4 3 .2 7 6 .4 77. 1 9 4 .3 9 0 4 .1
17
19
32. 1
34. 8
3 2 .5
35. 1
9 3 4 .3
A
9 3 4 .9
9 2 6 .4
A
A
8 5 .5
9 3 .6
2 1
23
* 3 7 .5 3 7 .3
9 1 6 .9 9 1 7 .5 A
A
101.3
10 8 .6
Vq = 85994. 6 c m
B 1 = 1. 398
Q Q
P 12 + R 23
Not
R e so lv a b le
D ' = 6 X 10'
v
A Sam e a s in 1 - a(F^)
* Sam e a s in 1 - a (F 3 )
T A B L E 1 - a ( F 1)
(tt 2p)(3pa )3 nn-X 3 S '(0 -0 )B a n d a tll6 2 A
g u 0 g _____
n
n
Vq = 85902. 5 c m
- 1
R Q 12(+P
1+ P R 13)
N P
13 Q 1 + Q R 1 2 ° P 1 2 ,+ ° Q 13>
N Obs Cal Obs Cal Obs Cal Obs Cal
1 A 85917.
9 A 8 5 9 0 2 .4
* 8 5 9 0 0 .0
8 5 8 8 9 .9
3
A
972. 8 85901. 7 9 0 1 .5 A 8 5 8 9 0 .0 893. 9 8 9 3 .7
5 85936.
9
937. 1 * 9 0 0 . 0 899. 9 A 8 7 7 .6 8 8 7 .3 8 8 6 . 7
7 45. 7 945. 7 8 9 7 .3 897. 7 8 5 8 6 4 .5 864. 5
878. 9 879. 1
9
53. 3 953. 5
A 894. 8 8 5 0 .3 850. 8
Not
8 7 0 .2 870. 8
1 1
A
9 6 0 . 6 8 9 1 . 2 8 9 1 . 2
8 3 5 .9 8 3 6 .5 * 8 6 1 .7 861. 8
13
A 967. 0 * 8 8 7 .3 8 8 6 . 8 8 2 1 .3 8 2 1 .4
R eso lv a b le 8 5 2 .6 852. 1
15
A 972. 6 8 8 1 .8 881. 7 8 0 5 .6 805. 5 841. 8 841. 7
17 8 7 5 .8 8 7 5 .9 788. 8
789. 0 830. 9 830. 7
19 A 8 6 9 .4 7 7 1 .4 771. 7 818. 9 819. 1
2 1
8 6 1 .7 862. 1 753. 5 753. 8
A 806. 7
23
A 853. 9 * 7 3 4 .9 735. 1 7 9 3 .5 7 9 3 .6
25 8 4 4 .6 845. 1 7 1 6 .0 7 1 5 .6
7 7 9 .9 779. 9
27
7 6 5 .7 7 6 5 .6
29 750. 5 7 5 0 .4
31
* 7 3 4 .9 734. 8
A Sam e as in 1 -
* S am e a s in 1 - a (F 3 )
B^ = 1 .3 5 2
= 2 .5 X 10
-5
V0 =
Bv
85902. 8 c m - 1
= 1 .3 5 2
= 4 . 7 X 10~ 6
00
19
b. (1-0) Band at 1136 A:
T h is is one of the two m o s t d iffu se bands (another one at 1088
A) an a ly zed in th is reg io n , w h ich show d is tin c tiv e ly th ree h ea d s. Since
the rotation al lin e s a r e v e r y d iffu se th e ir w a v e le n g th s w e r e m e a s u r e d
f r o m a d is p e r s io n cu rv e g r a p h ic a lly and a n a ly s is w a s done fo r the two
3 3 3 -
h igh er subbands ( IIj - X E ). T ab le 1-b. The m o le c u la r c o n
stan ts g iv en in the table a r e ap p ro x im a te e s tim a tio n s fr o m the a s s ig n e d
s s
b r a n c h e s . T h er e a r e only four b r a n c h e s o b s e r v e d . The R„_ + Q . .
5 L o 1
b ra n ch (es) and Q . + ° P , „ b r a n c h (e s) a r e l e s s c e r ta in than the other
tw o, s in c e th ey g iv e so m ew h a t s c a tte r e d v a lu e s rath er than
sm o o th ly changing"ones.
18
The iso to p e 0 a b so rp tio n sp e c tr u m sh ow s a sh ift of about 150
C *
c m * fo r th is band, indicating a v ib r a tio n a l quantum n u m b er of one
i
(v = 1 ) . The e ffe c tiv e p r in c ip a l quantum num ber n* y ie ld s a v a lu e of
3. 13. F r o m th is v a lu e and v a lu e of the spin coupling con stan t A
(« 1 0 0 c m *) e stim a te d fr o m the d iffe r e n c e of the band o r ig in s , one
h as conclu ded that th is band is the n ex t h igh er m e m b e r of the band at
1162 A (Sec. 1-a). The A Gx v a lu e (d ista n ce b etw een v ib r a tio n a l le v e ls
0 and 1 ) is then rou gh ly 1 9 9 0 c m \ a r e a so n a b le v a lu e co m p a red w ith
that of the s e r i e s lim it (« 1873 c m ^). H o w e v e r, the v a lu e (= 1 .5 2
c m is quite d iffe r en t fr o m that of the (0 - 0 ) band (B^ w 1. 4 c m )•
2 0
N
T A B L E 1 - b
( t t 2p)(3pa ) 3 n - X 3 E~ (1-0) Band at 1136 A
g ^ u g __________________
R 32+ ° 3 1 Q3+ P 32
R
Q
21
Q
23
1
3
5
7
9
11
13
15
17
88096
+ 105
112
118
131
139
(88082)
(79)
(75)
(69)
(71)
(67)
87995
88004
11
20
28
37
45
53
87981
(78)
(74)
(71)
(68 )
(65)
(62)
(59)
V q = 88087 c m * Vq = 87986 c m *
B ' « 1 .5 5 B 1:
V - 4 V
D 'w 10
v
tO v e r la p p e d by e m is s io n lin e
( ) See T ab le 1 - a (F 3 )
2 1
1 3 -
2. (t t 2p) (4pa ) II - S Bands at 1152, and 1125 A:
g ^ u' u g_________________ '______________
a. (0 -0 ) Band at 1152 A:
B e c a u s e of its strong in te n sity , w h ich w ill be d is c u s s e d in S e c -
3
tion V (band at 1154 A ), th is band w as thought to be a (c a s e b) -
3 _
Eg tra n sitio n at f ir s t . T h er e a r e fiv e b r a n c h e s o b se r v e d , R, P ,
(^ P + ^ R ), SR, and ° P . A m ong th em , ° P b ran ch is e x tr e m e ly w eak.
13
The c a lc u la ted in te n s itie s u sin g B u d o's equation s show that for a
3 3 -
nu (c a se b) - E^ tra n sitio n , (in p r a c tic e , the upper state is not e x a c t
c a s e b, but c lo s e to c a s e b, m ean in g Y is not ex a ct z e r o but a sm a ll
s o
n u m b er, Y = 1. 5 is u se d in the calcu lation ) the R and P b r a n c h e s
should be e x tr e m e ly w e a k («1% of that of R or P b r a n c h e s). T h er e
s s s
a re a ls o two R b r a n c h e s , ^ l ’ anc^ ^32* d ° se ex a m in a tio n show s
g
that the R b ran ch o b s e r v e d is d e fin ite s in g le t w h ich a ls o has c o m p a r
able in te n sity a s the R b ran ch . In addition, the R b ran ch o b se r v e d e x -
R
h ib its a ls o a sin g le t or a doub let (R, Q of d iffe r en t in te n s itie s ) rath er
than a m o r e c o m p le x tr ip le t str u c tu r e (R^, R £, R^ and s a te llite
3
b r a n c h e s). At the s a m e tim e , th e re a r e th r e e (npa ) II (c a se a) -
u u
3 - o
X E bands (1162, 1155, and 1121 A) o b s e r v e d in this r e g io n w ith r e a -
S
so n a b le c e r ta in ty . It is not lik e ly that th e re a r e two d iffe r en t coupling
c a s e s (a and b) r e s u lte d fr o m the sa m e e le c tr o n ic con figu ration (it 2 p)
6
(npa ) w ith c lo s e n v a lu e s (n eq u als 3 and 4). C on sequ en tly, the p o s
s ib ilit ie s of the upper sta te being a (c a s e b) is u n lik ely , but a
is con clu d ed .
T he l is t of a ll the o b se r v e d b r a n c h e s a r e g iv en in T a b le s
II-a(II ) and II-a(n*). (The s p e c tr u m is show n in F ig u r e 5 -a ). One
s e e s that th ere a r e d iffe r e n c e s in the m o le c u la r co n sta n ts for the II
and the II* s ta te s , in d icatin g a slig h t X-type doubling c a u se d probably
18
by the neigh b orin g s in g le t £ s ta te s . The iso to p e 0 sh ift of th is band
L d
is about 35 c m \ The v ib r a tio n a l quantum nu m b er is thus z e r o ,
w h ich y ie ld s a n'1 ' of 3. 23.
TABLE 2 - a(n+)
(t t 2p)(4pa ) X n - X^E (0-0) Band at 1152 A
g ^ u' u_______ g _________________
, - 1
R (c m ) (QP +QR )(c m _ 1 ) ° P ( c m 1)
N Obs Cal Obs Cal Obs Cal
1 - 8 6 8 5 9 .1 8 5 9 .6 8 6 8 4 3 .7 8 6 8 4 3 .5
3 874. 2 874.3 846. 2 845. 2 8 6 8 2 8 .3 829. 1
5 8 9 0 . 9 8 9 0 .4 848. 5 8 4 8 .4 820. 2 8 1 9 .4
7 908. 3 907. 9 853. 0 853. 0 8 1 0 .4 811. 0
9
9 2 6 . 8 9 2 6 . 8 * 8 5 9 .1 859. 0
804. 2 804. 2
1 1 946. 7 947. 1 8 6 6 . 5 8 6 6 . 5 798. 5 798. 7
13 9 6 9 .2 9 6 8 . 8 874. 9 875. 3 e m is s io n 794. 7
15 992. 0 9 9 1 .9
884. 7 885. 6 7 9 1 .4 792. 0
17 8 7 0 1 6 .2 0 1 6 .4 8 9 6 . 8 8 9 7 .2
19
042. 3 042. 3
2 1 071. 0 069. 5
+VQ = 86841. 1 c m " 1
B ' = 1. 615
v ,
D ' = 6. 0 x 10"
v
-J-V q h e r e i s the e ffe c tiv e e n e r g y of K' = 0 le v e l, sin c e II state
c o n s is t s of K odd ro tation al le v e ls only.
* S ee T ab le 1 - a ( F 3 )
24
TABLE 2 - a(n“)
(r r g 2p)(4pau )1 n i - 0 -0 ) Band at 1152 A
N R , R ,
P , P
obs c a l obs c a l
1 8 6 8 4 8 .5 8 6 8 4 8 .5
3 8 5 6 .4 8 5 6 .2
A
8 6 8 3 4 .1
5 8 6 6 . 5 8 6 6 . 2 (8 3 0 .2 ) 830. 8
7 877. 3 8 7 7 .1 (829. 1) 828. 8
9 8 8 8 . 8 8 8 9 .4 (8 2 8 .3 ) 8 2 8 .3
1 1 902. 8 903. 0 (8 2 8 .5 ) 829. 0
13 * 9 1 7 .7 9 1 7 .9 (831. 0) 8 3 1 .2
15
A
934. 1 A 8 3 4 .6
17 9 5 2 .0 9 5 1 .5 839. 8 839. 8
19 9 7 0 .5 9 7 0 .2
A 844. 9
2 1
A
9 9 0 .1 853. 0 8 5 2 .6
23 8 7 0 1 0 .3 8 7 0 1 1 .1
25 0 3 3 .3 3 3 .2
27 5 5 .1 5 6 .4
VQ = 86841.7 cm"1
B' = 1.611
r _ 5
D 1 = 1.4X10
A S e e T able 1 - a (F 3 )
* S e e T ab le 1 - a(Fg)
( ) S ee T ab le 1 - a(F-j)
1 ^ -
u
R q
15 1
1 —r i i i i n
P Q
■ s :
S. 9 1
R “l— i— i— i —i
3
i 1 1 i i
°P+°R
13 O n
T - r r
.1 V-.
*2 £&
I I I I I I I I ! ° p + ° D
R, + R2 + R3
■ 1 1 ___ I ___ I ___ I___l___l— I — I —l __l_I — I i l I I III- o,
F ig u r e 5 - a . 1£ +, 3 S " , 1E 8t *11 - X 3£ B ands in the
* u u u u g
R eg io n 1 1 5 5-52 A
to
b. (1-0) Band at 1125 A:
T h is is another forb id d en band o b se r v e d w ith a p p recia b le in ten -
R
sity . T h ere a r e fiv e b r a n c h e s o b s e r v e d w h ich a r e (R + Q) and
(P + ^*Q) b r a n c h e s w ith upper sta te and SR , ° P , and ( Q + ^ P + ^R )
b r a n c h e s w ith upper state *11*. T h ey a r e lis t e d in T able 2 -b . A ll the
rotation al lin e s appear to be d iffu se . The (P + ^Q) b ranch and
(Q + ^ P + ^R ) b ran ch a r e not r e s o lv e d . The SR and (R + **Q)
b r a n c h e s a r e o verlap p ed by the ad jacen t band at th eir sh o r te r w a v e
len gth sid e. F ig u r e 6 -a sh ow s the sp e c tr u m and the rotation al a s s ig n
m en t. The ° P b ran ch sh ow s d is tin c tiv e ly in the high p r e s s u r e s p e c
tru m . F o llo w in g the rea so n in g g iv en in 2 - a and the fa ct that ° P
b ra n ch ap p ea rs to be sin g le t, the upper sta te is b e lie v e d to be *n
rath er than (c a se b). F o r a (c a s e b) - tra n sitio n , the ° P
u u g
b ra n ch is doublet in addition to a w eak s a te llite b ran ch (s e e appendix).
\ - t y p e doubling a p p e a r s to b e p r e s e n t, sin c e d iffe r e n c e s in
rotation al co n sta n ts a r e o b se r v e d for the *11 state and *n* state,
u u
w h ich in d ica te s a sp littin g of the two s ta te s , w ith the *11 state higher
than the *11* sta te . T h ere is a * £ * state ( 4 -b) at about 375 c m *
u u
higher than the p r e s e n t upper state, w h ich p rob ab ly is r e sp o n s ib le for
3 + -1
the doubling. A nother state ( 3 -b) lo ca te d on ly 53 c m higher
than the p r e s e n t upper sta te p rob ab ly con trib u tes a s w e ll, sin c e s e le c -
20
tion rule AS = 0 fo r p ertu rb ation h old s only a p p ro x im a tely .
TA B L E 2 - b
( T T 2p)(4pcr )X n - X 3 E " (l-0 ) Band at 1125 A
g u u_______ g_______________________
xn
-
N R (c m
■s
P (c m
_1)
SR (cm P+ R (cm ) ° P (c m
Obs Cal Obs Cal Obs Cal Obs Cal O bs4 Cal
1 A 8 8 8 9 5 .7
T
8 8 8 8 6 . 1
A 8 8 9 0 6 . 6
t
88891. 2 A
8 8 8 7 6 .8
3 A 903. 7 Not 8 8 1 .3
A
9 2 0 . 1
1
892. 3 88867 8 6 6 .4
5 *88913. 8 9 1 3 .0 R e so lv e d 877. 8
A
9 3 4 .3
Not
8 9 4 .2 857 856. 8
7 A 9 2 3 .6 1 875. 6
A
9 4 9 .2
R e so lv ed
8 9 6 .9 848 848. 0
9 A 9 3 5 .4 888 7 4 .1 8 7 4 .4 A 9 6 4 .7
1
9 0 0 .3 840 840. 0
1 1 A 9 4 8 .4
N o t T
875. 0 * 8 8 9 8 0 .3 980. 7 i 9 0 4 .3 831 832. 5
13 A 962. 7
R e so lv ed
8 7 6 .6 9 9 7 .7 997. 1 8 8 9 0 8 . 8 908. 9 825 825. 6
15 A 978. 1 1
8 7 9 .4 A
8 9 0 1 3 .7 * 9 1 3 .8 913. 8 820 819. 1
17 9 9 4 .6 9 9 4 .7 8 8 8 8 3 .4 8 8 3 .4 2 9 .4 3 0 .3
A 9 1 9 .0
V = 88889. 0 c m - 1
Vq = 8 8 8 8 9 . 0 c m
1
B ' = 1 .
V
D' = 1.
V
599
4 X 10" 5
B ' = 1.
V
d ; 6
546
X io"5
A P o sitio n of lin e co v e re d by broad ab sorp tion lin e (s ).
* Blended
4 D iffu se lin e s , e n e r g ie s round off to c m
ts)
cA&jil
I
' 28
ly +
£ -m .
% A :•32-
13
— T“ ~i------r
Qj + Qa"
T
17
K'iv
i 'E O ;
It ■ ■ ■ * ■ ’ * ..■
¥ | f f
-'C l ■ :
'i: -1 -3 S !
: f : f > ■
; l» V . * •' - V * •
IJ&fca : * ..•& &
P „ ,+ P
rfr&r
v *
*Q
21
17
j i i i i.,i
_ i i__ i —i
— P Q
■ ■ ■ i i i i i-
3 o 17
Q+qP+°R
'TT»
F ig u r e 6 - a. 3£ + » 8?I T - X 3 S “ B ands
u u g
at 1125 A
29
18
The 0_ a b so rp tio n s p e c tr u m of th is and the r e s t of the bands
up to 1085 A have not b e e n o b se r v e d . It is r e a so n a b le to c o n sid er this
band to be the (1-0) m e m b e r , s in c e the n* obtained for v 1 = 1 is 3 .2 5 ,
v e r y c lo s e to that of band at 1151 A (.2-a , n* = 3 .2 3 ) . The & G ± is thus
s
2055 c m a ccep ta b le co m p a red w ith that of the s e r i e s lim it. The
in te n s ity of the p r e s e n t band ap p ea rs to be w ea k er than the (0 - 0 ) band.
2 24
A lb e r ti, et al, and Y am aw aki and Ogawa h ave o b se r v e d an
a b so r p tio n band of upper sta te (4pa^) ^11^ lo ca te d at about 350 c m
h igh er than the p r e s e n t state and a s m a lle r rotational constan t
(« 1 .4 5 c m *). To ex p la in the s m a lln e s s of the rotation al con stan t for
a R ydberg sta te , Y am aw aki and Ogawa had su g g e ste d that the state
w a s a r e s u lt of a sta b le R yd berg sta te c r o s s in g w ith a r e p u lsiv e sta te,
s a m e type of in te r a c tio n in d icated in S ectio n 1-a, band at 1162 A. One
p o s s ib le explanation to the p r e s e n t redundant state m igh t be that it
is contributed m a in ly by the o r ig in a l sta b le R ydberg state slig h tly p e r
turbed by the r e p u lsiv e sta te (se e F ig u r e 4 - a ). The d iffu s e n e s s of the
o b se r v e d band and the la r g e r valu e a g r e e w ith this explanation. If
th is explanation is c o r r e c t, it s e e m s that su ch two c r o s s in g sta te s
s till reta in th eir own c h a r a c te r is t ic s e x c ep t at the neighborhood of the
in te r s e c tio n . T h is is in fa c t c o n s is te n t w ith the F ran k -C on d on p r in c i
p le in perturbation?^
3. (it 2p)(4prr ) ^£ + - B ands at 1148, and 1125 A:
g r * u u_______ g________________________________
30
a. (0-0) Band at 1148 A:
T h is is a v e r y w eak and d iffu se band (se e F ig u r e 5 -b ). The
e n e r g ie s of the rotation al lin e s w e r e m e a s u r e d w ith the co m p a ra to r
but the v a lu e s rounded off to c m ^ a r e g iv en for the a s s ig n e d b r a n c h e s.
B e c a u s e of its c o m p le x stru ctu re and d iffu s e n e s s , it w a s one of the
m o s t d ifficu lt bands a n aly zed . It h as b een concluded that th is is a
3 + s s
forb idd en band of upper sta te £ . Six b r a n c h e s, R , Q,»
U J u ul X
Q , ° P , and ° P , a r e o b se r v e d . T h ere a r e a lso w ea k er and u n re-
J lu fa J
so lv e d s a te llite b r a n c h e s ( s e e Appendix) that a r e ig n o red . The r o ta
tion al con stan ts B' obtained for the f ' state and F' state a r e d ifferen t,
v 1 3
The o b se r v e d b ra n ch es and rotation al co n sta n ts a r e lis te d in T able
2
3 - a. The A„F"/(K+jb-) v a lu e s c a lc u la ted a r e quite s c a tte r e d . T hus,
f a
no D 1 valu e is obtainable. The Q v s K(K+1) p lot show s that th ere is a
17
s m a ll h om ogen ou s type of p ertu rb ation p r e s e n t, but no perturbing
sta te i s o b se r v ed .
18
The iso to p e 0^ sh ift of th is band is z e r o , indicating v' = 0.
n* ca lc u la ted is 3 .2 7 .
C om paring the B^ of th is band and its vib ra tio n a l quantum
n u m b er w ith that of the "1144" band o b se r v e d by Ogawa and
3
Y am aw aki, w h ich w ill be d is c u s s e d la te r (Section 4 ), one h as c o n
cluded that the upper state of th is band is the tr ip le t state resu ltin g
' I + ILL
3 1 3 op
i i mi “
3 z :
21 1
— I --------1 I 1 ----- 1 ---- 1 ----TTTTT
15
— r~ 1 -------1 ----- 1------ 1 ------r
1
• i - " i "32
21
— r~ t r
1 s „
t 1-----1 -----r R
15 1 S r
1 ------------------ 1 ----------------1 ------------- 1 - " I---------------- 1 ---------------1 ---------------T * '2 1
£ $ & ’ > *
_L _
21
J I 1 -----1 ___I _ _ I ___L i-U
21
1 ------1 ----- 1 ----- 1 — 1 1 1 1 ‘J > Q 3
1
3
'23
F ig u r e 5 - b . Bands at 1148 & 1144 A
u u g
U )
32
TA BL E 3 - a
(rr 2p)(4prr ) 3 S +- ^ S " (0-0) Band at 1148 A
g y u' u g________________________
N
C O
X z ° P 1 2 ° P 23
1 87139
87136 87124
3 157 151 128 87124 (87108) 87110
5 177 172 132 128 99 99
7 2 0 0 194 139 (137) 93 93
9 219
215 149 147 ( 8 8 ) (91)
1 1 242 238 161 157 (87) (90)
13 268 263 172 168 ( 8 8 ) (87)
15 302 293 189
182 (87) (87)
17 323 208 2 0 0 (92) (90)
19
228 219 (99)
2 1 251 240
+V0 (F i ) = 87124 c m " 1
V 0 (F^) = 87121
B' = 1 .7 1 2 c m " 1 (Fi )
v 1
b ' = 1 .6 8 3 c m ' 1 ( F ')
v 3
( ) S ee T able 1 - a (F 3 )
+The band o r ig in s for the F^ and F^ le v e ls a r e defined a s the
h eigh ts of the F^ and F^ le v e ls r e s p e c t iv e ly in the K* = 0 le v e l (a
v irtu a l le v e l) m e a s u r e d fr o m the j" = 0 and N n = 0 in the ground
sta te .
f r o m the sa m e e le c tr o n ic con figu ration , and the "1144" band is
1 + 3 +
E in ste a d of a E a s s u g g e ste d by Ogawa and Y am aw aki.
34
b. (1 -0 ) Band at 1125 A:
T h is band a p p e a r s to b e m u ch m o r e str o n g e r than the (0 -0 )
band (s e e F ig u r e 6 -a ). It is o v erla p p ed p a r tly on both s id e s by the
s s
adjacen t b an d s. T h er e a r e th ree b r a n c h e s o b s e r v e d , R + R ,~ ,
u 1 J u
Q l + Q^, and ° P j 2 + °^ > 2 3 ’ aS ^ stec* ’■ n T ab le 3 -b .
F r o m the ro tation al co n stan t and the n* v a lu e (3. 27) obtained
b y using v 1 = 1 , it is r e a so n a b le to con clu d e that the p r e s e n t band is
the (1 - 0 ) m e m b e r , s in c e th ey a re v e r y c lo s e to that of the (0 - 0 ) m e m -
1 I 3 ~
b e r at 1148 A . The (1 -0 ) m e m b e r of the (t t 2p)(4prr ) £ - X S p r o -
g r c u u g
g r e s s io n has a ls o b e e n o b s e r v e d at about 322 c m ^ h igh er than this
band ( s e e S ectio n 4 -b ). T h is is another e v id e n c e supporting the p r e
se n t a s s ig n m e n t. T he AG X turns out to be 1821 c m \ c lo s e to that of
s
the s e r i e s lim it.
c. (2 -0 ) Band at 1101 A:
T h is is a ls o a stron g band (s e e F ig u r e 8 ) fo r a forb id d en tr a n
sition . Its d iffu s e n e s s s e p a r a te s th is band fr o m the group of bands of
4f c o m p le x w h ich a r e lo c a te d n e a r at its lo n g e r w a v elen g th sid e (S e c
tion 8 ). The s a m e th r ee kind of b r a n c h e s a r e o b se r v e d a s in 3 -b .
3 3 O
A m ong th e m , R + R Is th® s tr o n g e s t but quite d iffu se, P ^ +
° P is w ea k and overla p p ed w ith the ad jacen t band. T h ey a r e lis te d
1 C t
in T able 3 - c , to g eth er w ith the m o le c u la r c o n sta n ts.
T A B L E 3 - b
(t t 2 p ) ( 4 p n ) 3 E +- X 3 £ ( 1 - 0 ) B a n d a t 1 1 2 5 a
g u u g _____________________
S r 21+SR32
(0 ^ 3 )
° P ° P
23 12
N Obs C al Obs Cal Obs Cal
1 * 8 8 9 6 1 . 8 8 8 9 6 1 . 6 8 8 8 4 5 .0 8 8 9 4 4 .9
3 9 7 7 .3 977. 3 8 4 7 .4 9 4 7 .2 A
8 8 9 3 0 .5
5 9 9 4 .7 94. 7 51. 7 5 1 .4 88820. 9 821. 3
7 A
8 9 0 1 3 .9 5 7 .3 5 7 .4 813. 8 814. 0
9 * 8 9 0 3 4 . 6 34. 8 65. 6 65. 1 808. 8 808. 5
1 1 * 5 7 .7 57. 2 74. 3 7 4 .4 A
804. 7
13 * 8 1 .2 81. 0 8 5 .4 8 5 .4
A
2 . 6
15 * 97. 7 9 7 .7
A
2 . 1
17
3. 0
B 1 = 1. 672 c m - - * -
v
D ' = 5 X 10- 5
v
Vq = 8 8 9 4 4 .4 c m *
* See T ab le 1 - a ( F 3 )
A S ee T ab le 1 - a ( F 3 )
T A B L E 3 - c
( T T 2p)(4pTT ) 3S + - x V (2 -0 ) B an d a t 1101A
v g ^ y u u _g ___________________________
N
R 2 1 + R 32
Q +Q
1 3
° p + ° p
23 i;
1 9 0 8 2 2 . 2 9 0 8 0 5 .2
3 836. 3 807. 1 90788. 8
5 8 5 2 .7 8 1 0 .4 780. 9
7 870. 1 8 1 5 .1 7 7 2 .9
9 (8 8 8 . 9) (8 2 1 .2 ) 7 6 6 .4
1 1 (908. 8 ) 8 2 8 .6 7 6 0 .5
13 (837. 0 * 7 5 6 .6
15 7 5 2 .3
ii
o
>
9 0 8 0 5 .2 cm -1
B ' =
V
1 .6 1 8
D ' =
V
1 0 - 5
) S e e T ab le 1 - a (F 3 )
T he n* v a lu e s ca lc u la ted w ith v' = 1 and v' = 2 a r e 3 .6 1 and
3 .2 7 , r e s p e c tiv e ly . S in ce the (1-0) m e m b e r has b een o b se r v e d
a lre a d y , the v ib ra tio n a l quantum nu m b er is m o s t lik e ly to be 2. H ow
e v e r , the rotation al con stan t B 1 (=1. 618 c m *) is m u ch s m a lle r than
v
the other m e m b e r s o b se r v e d . The A G ^ ^ y ie ld s a v a lu e of 1855 c m \
r e a so n a b le com p arin g w ith that of the A G ^
38
4. (it 2p)(4pn ) *£ + - X^£ B ands at 1144, and 1120 A:
g r u' u_______ g_________________ '_______________
a. (0-0) Band at 1144 A:
A s m en tion ed in the la s t s e c tio n ab ove, th is band has b een
3 s
an alyzed by Ogawa and Y am aw aki. The o b s e r v e d b r a n c h e s R, Q,
and ° P a r e lis t e d in T ab le 4 - a . The B ^ v a lu e obtained is slig h tly
s m a lle r than p r e v io u s ly r e p o rted (1. 701 c m * com p ared w ith 1. 706
c m Ogawa and Y am aw aki s u g g e ste d that the upper state w as a
3 4 * 1 4 *
£ rath er than a £ sta te, b a se d on the B v a lu e s co m p a red with
u u v
2 +
th o se of the a and |3 s y s t e m s , and the X I T state of O^. H ow ever, the
2
v ib ra tio n a l quantum num ber of the X n has to b e in c r e a s e d by one
22 23
b a se d on m o r e r e c e n t e x p e r im e n ta l r e su lts . ’ In addition, the
sharp sin g le lin e ap p ea ra n ce of the sp e c tr u m (F ig u re 5-b) (se e A p p en
d ix for the sc h e m a tic d ia g r a m of the tra n sitio n s) in d ic a te s the upper
3 +
state a s in g le t rath er than a tr ip le t. A t the sa m e tim e , the £ band
o b se r v e d at 1148 A (Section 3 -a ) m a k e s the s in g le t a s s ig n m e n t quite
r e a so n a b le .
D ue to the w eak in te n sity , th is band w a s not o b se r v e d in the
1 8
0 a b sorp tion sp e c tr u m . The vib ra tio n a l quantum num ber is
L a
a s s u m e d to be z e r o , sin c e the upper state is c o n s id e r e d being r e
su lted fr o m the s a m e e le c tr o n ic con figu ration a s that of the band at
1148 A (Section 3 - a), n* y ie ld s a v a lu e of 3. 32.
39
TA B L E 4 - a
(T T 2p)(4pTT ) 1E+- X3S" (0 -0 ) B an d a t 1144 A
g u u R_______________________
N Obs C al Obs C al Obs
1 8 7 3 8 7 .5 8 7 3 8 7 .7 8 7 3 7 0 .7 8 7 3 7 0 .7
3 404. 6 4 0 4 . 0 373. 7 373. 3 A
5 4 2 2 .4 4 2 2 .3 3 7 8 .4 378. 1
A
7 442. 8 4 4 2 .7 385. 0 384. 9 87340
9
4 6 5 .2 465. 1 394. 0 393. 8
A
1 1 * 4 8 9 .9 4 8 9 .7 * 4 0 4 .6 4 0 4 . 8 A
13 516. 3 516. 3 417. 9 417. 9
A
15 5 4 4 .7 544. 8 433. 0 433. 0
17 5 7 5 .2 575. 3 449. 8 4 5 0 .1
19 607. 9 6 0 7 .9 4 6 8 . 8 4 6 9 .2
2 1 6 4 2 .5 6 4 2 .3 * 489. 9 490. 3
23 678. 8 6 7 8 .6
VQ = 87370
, - 1
. 2 c m
B ' = 1 .7 0 1
V
D ' = 1 .2 X 1 0 " 5
V
A S e e T able 1 - a ( F 3 )
r See T able 1 - »(f 3 )
C al
87356. 3
3 4 7 .4
340. 7
336. 1
3 3 3 .5
333. 0
334. 6
338. 3
4 0
b. (1-0) Band at 1120 A:
The sp e c tr u m of th is band r e s e m b le s c lo s e ly to that of the
(0-0) m e m b e r at 1144 A (F ig u re 6 -b ), p art of w h ich is overla p p ed by
the adjacen t strong band at its lo n g e r w a v elen g th sid e (Section 7).
The th ree o b se r v e d b r a n c h e s a r e lis t e d in T able 4 -b .
U sing v' = 1, the n* c a lc u la ted y ie ld s a valu e of 3. 32. C o m
paring this v a lu e and rotation al con stan t (=1 . 6 9 8 c m ^) with th o se
of the (0-0) m e m b e r (n* = 3. 33, B^ = 1. 701 c m *) it is c e r ta in that
the p r e s e n t band is the (1 -0 ) m e m b e r of the s a m e p r o g r e s s . The
&GX v a lu e, 1 8 9 6 c m * c a lc u la ted is a g r e e a b le .
s
' s :
25
1 7
i r
— i—
I I I I I i mi I
19 13
■23
T IT
15 1 Pn
i i i I i i i i kq 2 1
m m
m
m
2/S-
t R .
■ 3 1
I l.l-l-lll
17
i. i 1.1 iii
Q3 +^32
R„ I ' I I I I 1 i 1 1 LJlllrf.
15 1 1
_i I i i i
9 1
*'32
19
■ i i > i i i i i
l > 1 1 1 1
3 13
rQ 12+ p , + p R .3
"TTu.
3 1 + 3 - o
F ig u r e 6 - b . II ,& E - X E Bands at 1121 & 1120 A
u u • g
42
T A B L E 4 - b
(t t 2p)(4pTT ) 1S +- X 3S “ (1 -0 ) B an d a t 1120 A
g r n ' u g________________________
SR (QP + QR) ° P
N Obs C al Obs C al Obs C al
1 * 8 9 2 8 4 .0 892 9 3. 8 * 8 9 2 6 7 .3 8 9 2 6 7 .0
3 * 3 0 0 .1 300. 0 * 2 6 9 .7 2 6 9 .4 A 89252. 4
5 318. 0 3 1 8 .1
A 274. 1 A 243. 5
7 * 3 3 8 .6 338. 3 2 80. 6 280. 8 8 9 2 3 6 .2 236. 7
9
* 3 6 0 .3 360. 3 A 2 8 9 .4 2 3 1 .7 231. 9
11 3 8 4 .4 3 8 4 .2 * 300. 1 300. 0 228. 5 229. 0
13 4 09. 8 409. 9
3 1 2 .4 3 1 2 .4 228. 5 228. 2
15 4 3 7 . 1 3 3 7 .2 326. 6 326. 6 228. 5 229. 2
17 4 6 5 .7 4 6 6 . 0 342. 7 342. 5
19
* 3 6 0 .3 359. 8
B ' = 1. 698 c m *
v
D ' = 4 .2 X 1 0“5
v
Vq = 89266. 3 c m *
A See T ab le l - a ( F 3 )
^ e e T able l - a ( F 3 )
43
1 i 3 - o
5 . (t t 2p)(3pTT ) E - X E (6-0) Band at 1155 A (a System ):
_______g u u_______ g________________________________________
3 3 -
T h is band is o verlap p ed w ith the ad jacen t - X E^ band
p a r tia lly at its sh o r te r w a v elen g th sid e (F ig u re 5 -a ). At high p r e s
s u r e , the sp e c tr u m sh ow s the ° P b ran ch standing out at the lo n g e r
w a v elen g th sid e. At n o r m a l p r e s s u r e the sp e c tr u m is rath er w eak,
a lm o s t c o m p le te ly o b sc u r e d by the ad jacen t strong band. B a s e d on
the o b s e r v e d ° P b ran ch , the a s s ig n m e n t of the SR and (^ P + ^R ) a re
g iv en fr o m the com b in ation r e la tio n s. T h ey a r e lis t e d in T ab le 5
T he Q b ran ch is not g iv en in the tab le, s in c e a ll the m e m b e r s a r e each
about 2 c m * lo w e r than that of (^ P + ^ R ) b r a n c h e s and w h ich a r e not
3 2
r e s o lv e d . Ogawa and Y am aw aki, and A lb e r ti, et al have studied the
3pit ^e " * " - X^E (a s y s te m ) in the lo n g e r w a v elen g th sid e of this r e -
u u g
gion. It is p o s s ib le to in clu d e the p r e s e n t band a s the (6-0) m e m b e r
in the p r o g r e s s io n (T anaka's p r o g r e s s io n II). T h is band is not ob-
18
s e r v e d in the 0 a b so rp tio n s p e c tr u m , w h ich in d ic a te s that probably
the v ib ra tio n a l quantum num ber is r e la t iv e ly high, and thus the iso to p e
sh ift is a rath er la r g e v a lu e . U sin g v' = 6 , the n* valu e obtained is
2. 26. C om paring w ith that of the a s y s t e m (n* = 2. 28), one s e e s it is
a c c e p ta b le a s the (6-0) m e m b e r . H o w ev er, the rotation al con stan t
b' v a lu e g iv en in T ab le 5 is s m a lle r than e x p e c te d for the a s y s te m .
T h is could p rob ab ly be accou n ted fo r by the s a m e in te r a c tio n that
T A BL E 5
(tt 2p)(3pT T ) - xV (6-0) Band at 1155 A (a s y s te m )
g r r u u_______ g____________________________________
o C > Q„ s „
P P + R R
N Obs Cal Obs Obs
1 (8 6 6 5 3 .9 ) (86669. 0 )
3 8 6 6 3 9 .5
8 6 6 3 9 .5 (6 5 4 .6 ) (681.9)
5 629. 1
628. 8 (656. 1) (695. 5)
7 6 1 8 .3 6 1 8 .7 (658. 1) (7 0 9 .6 )
9
6 0 9 . 2 609. 2 (6 6 0 .7 ) (724. 3)
1 1 600. 3 6 0 0 .4 (6 6 4 .0 )
13 5 9 2 .2 5 9 2 .2
15
Vq = 86653. 7 c m *
B '= 1 .5 1 7
v
D 1= 1. 5 X IQ' 5
( ) S ee T ab le 1 - a (F 3 )
4 5
c a u se d the d iffu s e n e s s of the (5-0) m e m b e r of the a s y s te m (no
ro ta tio n a lly a n alyzed r e s u lt availab le) w h ich is overlap p ed by the
"third band" at 1172 A.
3 - 3
6. (t t 2p)(3pTT ) E - X E (0-0) Band at 1154 A:
g e u 7 u_______ g ___________________
T h is band and the two ad jacen t bands (Section 2 -a , and
S ection 6 ) h ave r e la tiv e ly strong in te n s itie s (F ig u re 5 -a) am ong all
the bands an alyzed a s m en tion ed in S ection 2 -a , d e sp ite the fa c t that
the la tter two bands a r e forb idd en tr a n sitio n s . T h is p e c u lia r strong
in te n s itie s could be exp lain ed if one n o tic e s the strong d iffu se a b s o r p
tion bands at the lo n g er w a v elen gth sid e , the " lo n g est band" at 1244
O O o 3
A, the " secon d band" at 1206 A, and the "third band" at 1172 A, as
in d icated in S ection 1-a. The w a v elen g th r e g io n of the p r e s e n t band
and the adjacen t two bands could be co in cid en ta l w ith p o sitio n of the
fourth m e m b e r in the sp e c tr u m , if one a r r a n g e s the above lo n g e st,
secon d , and third bands in a p r o g r e s s io n . T he in te n s itie s a r e thus
enhanced c o n sid e r a b ly for the p r e s e n t band and the forb id d en bands.
T he sp e c tr u m h as a so m ew h a t d iffu se str u c tu r e . It ap p ea rs at
f ir s t to have a Q b ran ch , w h ich is not tru e after c lo s e exam in ation ,
sin c e no app rop riate P b ran ch could be obtained. At the sa m e tim e ,
3
the upper state w ill b e a (c a s e b) if th ere is a Q b ran ch p r e s e n t.
3 3 -
T h is i s v e r y u n lik ely, sin c e all the tr ip le t (npa 11^ - X E^ bands
o b se r v e d in the r e g io n of in te r e s t a r e of coupling c a s e (a) for the
upper state (as exp lain ed in S ection 2 - a ) . T hus, it has b e e n ten ta-
3 _
tiv e ly d ecid ed that the upper state of th is band is a E^ sta te. The
u n r e so lv e d R b ra n c h e s (R^ + R^ + R^) an(i P b r a n c h e s (P^ + + P^)
t
4 7
a r e lis t e d in T ab le 6 . The d iffe r e n c e s b etw een the o b se r v e d and the
ca lc u la ted v a lu e s p rob ab ly a r e c a u se d by the u n c e r ta in tie s of the m e a
su r e m e n ts of the d iffu se rotation al lin e s .
18 -1
The iso to p e 0^ shift of th is band is about 50 c m , indicating
a v' b etw een 0 and 1. F o r v' = 0 n* eq u als 3. 20; w h ile fo r v' = 1, n*
eq u als 2. 96. The la tte r valu e d o es not fit for a P e le c tr o n . N e v e r -
3 _
t h e le s s , the upper sta te being (4pTT^) E (v1 = 0 ) is not lik e ly e ith e r ,
3 _
b e c a u s e the band of upper state (4prr ) (v 1 = 1) o b se r v e d is at about
4000 c m ^ higher (Section 10, band at 1102 A ), w h ich is m o r e than
tw ice the a v e r a g e sep a ra tio n b etw een the rotation al le v e ls o b se r v e d in
this r e g io n (« 1 8 0 0 c m ^). To find the ap p rop riate n v a lu e (3 or 4) for
this P e le c tr o n , one s e e s that the B 1 (=1. 538 c m *) value is s m a ll for
a R ydberg sta te . It is thus s u g g e ste d that the upper state is probably
3 -
the r e s u lt of a sta b le R ydberg sta te c r o s s e d by the sh allow state B
at its inner lim b (F ig u re 4 -b ). The o r ig in a l state is then g r e a tly p e r
turbed and ap p earin g to a s s u m e the c o u r s e of the r e p u lsiv e sta te.
T hus, the e q u ilib r iu m in te r n u c le a r d ista n c e is sh ifted outw ard
(r a 1/ a/B ' ) and the v ib r a tio n a l le v e l is sh ifted up a s o b se r v e d in the
e v v
3 / / °
(3pa ) n sta te s (1162, 1136 A band s). The v ib r a tio n a l quantum
nu m b er bein g 0 or 1 a r e qual lik e ly , and n eq u als 3 for the e x c ite d p
e le c tr o n is con clu d ed .
48
T A B L E 6
( T T 2p)(4pT T ) 32 f - X 3E" (0-0) Band at 1154 A
g y * u m g_______________________
R l +R2 +R3
p x p j-p
1 2 3
N Obs C al _A_ Obs C al _A
1 8 6 6 8 1 .3 8 6 6 8 1 .9 - 0 . 6 8 6 6 7 3 .6 8 6 6 7 2 .5 1 . 1
3 689. 9 689. 0 +0 . 9 6 6 6 . 5 667. 5 - 1 . 0
5 6 9 9 .1 6 9 6 .9
+2 . 2 664. 0 663. 1 0 .9
7 707. 6 705. 6 +2 . 0 660. 4 6 5 9 .5 0 . 9
9
* 7 1 2 .6 714. 9 - 2 . 0 (6 5 8 .7 ) 656. 7
1 1 * 7 2 3 .5 724. 9 - 1 . 4 (6 5 2 .6 ) 6 5 4 .5
13 * 7 3 4 .9 7 3 5 .4 -0 . 5 (6 5 1 .6 ) 653. 0
15 (6 5 1 .6 ) 652. 2
V q = 86675. 5 c m *
B '= 1 .5 3 8
v
D ' = 3 .6 X 10- 5
A D iffe r e n c e of c a l. fr o m ob s.
* S e e T able 1 - a (F 3 )
( ) S e e T ab le 1 - a(F g)
49
1 - 3 -
7. ( t t 2p)(4prr ) E - X E (0-0) Band at 1153 A:
g y u u___ g ______________________
T h is band has no Q branch. The rotation al lin e s are r e la tiv e ly
sharp (s e e F ig u r e 5 -a ). B e c a u s e of the s im p le str u c tu r e , it is lik e ly
1 - 3 -
that the upper state is a E rath er than another E . The r e a so n for
u u
its strong in te n sity h as b e e n s u g g e ste d in the p r e c ed in g band at 1154
o
A.
R p 1 3
T h ere a r e four b r a n c h e s, R, Q, P , and Q fo r a E - E
u g
tra n sitio n (se e A ppendix fo r the s c h e m a tic d ia g r a m fo r the tra n sitio n ).
R p
The r e la tiv e in te n s itie s b etw een R and Q, and b etw een P and Q, as
18 R
a cco rd in g to K ovacs, in d icate that Q is str o n g e r than R and P is
p R
s tr o n g e r than Q. Thus (R + Q) b ran ch should b e shading tow ard the
lo n g er w a v elen g th sid e , and (P + ^*Q) the sh o r te r w a v elen g th sid e,
a ssu m in g they a r e not r e s o lv e d r e s p e c t iv e ly . It ap p ea rs not to be the
R R
c a s e fo r the (R + Q) b r a n c h e s. The rotation al a s s ig n m e n ts of the Q
b ran ch a r e p ick ed at the s h a r p e s t and s tr o n g e s t p o sitio n of ea c h lin e (s ).
The r e s u lt s a r e lis t e d in T able 7. The b ran ch in ste a d of P b ran ch
a r e lis t e d sin c e the e a r ly m e m b e r s of is o b s e r v e d to be str o n g e r ,
18
w h ich is co n tra r y to the th e o r e tic a l in te n sity d istrib u tion . In ad d i
tion, th ere is a strong and sharp lin e at the lo n g e r w a v elen g th sid e of
R
the Q(2) not bein g accou n ted fo r . D e sp ite the above ir r e g u la r it ie s ,
the upper state is m o r e lik e ly to be sin g le t than tr ip le t.
18 - 1
The iso to p e 0^ sh ift is a ls o about 50 c m as the la s t band. The
c h o ic e v' = 0 g iv e s a n* v a lu e of 3. 21, ap p rop riate for a 4p e le c tr o n .
50
T A B L E 7
(T T 2p)(4pn ) - X^E (0-0) Band at 1153 A
g y u 7 u g ________________________
Rv-w - 1 ,
Q (cm ) PQ (cm
- 1)
N Obs Cal Obs Cal
1 86737. 2 8 6 7 3 7 .4 8 7 7 2 7 .8
3 7 4 5 .2 7 4 5 .2 8 6 7 2 3 .5 723. 0
5 753. 9 7 5 3 .2 7 1 9 .6 7 1 9 .3
7 7 6 3 .9
764. 2 716. 5 716. 8
9
774. 6 775. 1 (7 1 5 .0 ) 7 1 5 .3
1 1 7 8 7 .0 7 8 6 .9
(7 1 4 .3 ) 714. 8
13 800. 0 7 9 9 .3 (7 1 5 .2 ) 715. 0
15 812. 0 811. 9 (7 1 6 .7 ) 716. 0
VQ = 86728. 7
- 1
c m
B 1 = 1. 589
V
D ' = 8 .4 X 10
V
-5
( ) S ee T ab le 1 - a (F 3 )
* S ee T ab le 1 - a (F 3 )
No o b se r v e d v a lu e
5 1
3 3 -
8 . (n^2p)(4pa ) 1 7 u (c a s e a) - X (1 -0 ) o r (0-0) Band at 1121 A:
T he sp e c tr u m of th is band is v e r y s im ila r to that of the band at
a 3 3 -
1162 A (Section 1 -a , 3po^ n - X £ )f w ith th ree d istin c tiv e heads
3
(F ig u re 6 -b ), ind icatin g a tr ip le t upper state n of Hund's coupling
c lo s e to c a s e (a). T h er e a re fiv e b r a n c h e s o b se r v ed for each spin
3 3 3
su b sta te, II^F ^), and IT q(F^). T h ey a r e lis te d s e p a r a te ly
in T a b le s 8 - (F^)* 8 - (F^), and 8 - (F^), tog eth er w ith the m o le c u la r
c o n sta n ts.
One can s e e fr o m the m o le c u la r co n sta n ts obtained, the ph e-
3
n om en on of \ - t y p e doubling in a n (c a s e a) sta te . Since the
3 - 3 +
sp littin g s b e tw e e n the II sta te s and n sta te s depend on the Q
15 - +
v a lu e s, the sp littin g s b e tw e e n the n and the n sta te s of ea ch of the
3
spin su b sta te s a r e d ifferen t. T his h as b e e n d e m o n str a ted in the n
u
state at 1162 A (Section 1-a) w h er e the sp littin g s only b e c o m e apparent
3
in the IIq(Fj) s ta te s (Q = 0 ), s in c e the sp littin g is the g r e a te s t in the
sta te of s m a lle s t f2. F o r 0 = 0, the sp littin g is independent of J,
w h ich sh ow s a d iffe r e n c e in band o r ig in s for the II and n* state and
a p p r o x im a te ly no d iffe r e n c e in the ro tation al co n sta n ts for the low J
3
l e v e l s . F o r II, (F„) (0 = 1) s ta te s , the sp littin g is p rop ortion al to
X b
J(J+1), w h ich is in d icated by d iffe r en t rotation al c o n sta n ts. F o r
3 2 2
^ 2 ^ 3 ^ ^ = ^ s ta te s , the splitting is p rop ortion al to J (J+ l) , w h ich
should a ls o show d ifferen t rotation al co n sta n ts a p p ro x im a tely . The
T A BL E 8 - (F )
(rrg2 p )(4 p g j (0-0) or (1-0) Band at 1121 A
II State
R
31
N
1
3
5
7
9
11
13
15
17
19
21
23
25
Obs
*89275.
A
304.
* 321.
* 338.
* 357.
A
397.
418.
Cal
892 7 5 .5
289. 6
3 0 4 .9
3 2 1 .4
3 3 8 .9
3 5 7 .4
376. 9
3 9 7 .3
4 1 8 .5
R
Q
32
Obs
8 9 2 59.5
2 6 1 .7
2 6 5 .5
A
A
A
A
5 300. 1
3 1 0 .4
5 3 2 1 .3
Cal
8 9 2 5 9 .1
261. 8
2 6 5 .6
270. 5
276. 6
283. 6
291. 6
300. 6
3 1 0 .4
3 2 0 .9
Obs
A
8 9 2 2 6 .4
2 1 8 .9
A
w ea k and
unre solved
Vq = 89257. 3 c m
B = 1 .5 8 7
v
- 1
C al
8 9 2 3 5 .2
2 2 6 .4
218. 7
212. 2
206. 7
2 0 2 .4
1 9 9 .0
196.5
1 9 4 .8
19 3 .9
n+ State
R
32
Obs
A
A
89280.6
A
302. 6
314. 7
328. 5
: 3 4 2 .7
3 5 7 .4
C al
8 9 2 6 4 .0
271. 8
280. 9
291. 1
3 0 2 .4
314. 8
328. 2
342. 7
358. 0
Q,
32
Obs
Vg = 89257. 3 cm
B ' = 1. 589
v
- 1
Cal
Not
r e so lv e d
89249. 6
245. 9
2 4 3 .5
2 4 2 .2
242. 1
243. 0
245. 0
247. 9
251. 8
* See T able 1 - a (F 3 )
A See T able 1 - a (F 3 )
3 .0 X 10 D ' = 2. 8
v
X 10
U 1
ts)
T A B L E 8 - (F )
3 3 -
(t t 2p)(4pcj ) n - X E (0-0) o r (1-0) Band at 1121 A
g u u______g ________________ _
II State
r q
2 1
P Q
23
N Obs Cal Obs Cal
1 (89169.3) 8 9 1 69.3
3 1 7 6 .4 1 7 6 .4
8 9 1 5 4 .9 8 9 1 5 4 .9
5 * 1 8 4 .7 184. 1 150. 1 150. 5
7 * 1 9 2 .0 1 9 2 . 6 146. 6 146. 8
9 2 0 1 . 6 2 0 1 . 8 143. 6 143. 8
1 1 2 1 1 .5 2 1 1 . 6 1 4 1 .2 1 4 1 .5
13 222. 3 2 2 2 . 1
A 139. 8
15 (2 3 3 .3 ) 233. 2
A 138. 8
17
A 13 8 .5
19 A 13 8 .6
VQ = 89161 . 0 c m ” ^
B ' = 1.531
V
D ' = 2 .0 X
V
1 0 " 5
R
2 1
Obs
8 9 1 7 8 .2
; 1 9 2 .0
205. 1
A
A
II+ State
Q Q
2l"*" 23 23
Cal Obs Cal Obs Cal
8 9 1 7 8 .5 A 8 9 1 6 3 .2
191. 7 8 9 1 64.5 164. 1
A 89148. 8
2 0 5 .5 (1 6 6 . 1 ) 165. 8 138.6 1 3 8 .2
2 2 0 . 1 (167. 7) 168. 2 128. 1 1 2 8 .4
2 3 5 .4 A 171. 3 119. 8 11 9 .3
A 17 5 .0
A 179.5
* 1 8 4 .7 184. 5
Not enough m e m b e r s to evaluate
sig n ifica n t d ifferen t vo and B^ D -J- v a lu es
fr o m that of II- state. T h ose of 11“ state
w e r e u se d for the calcu lated v a lu e s
* See T able 1 - a(F^)
( ) See Table 1 - a(F )
U i
w
TA BLE 8 - (F )
(TT^2p)(4pg^) 3 IIu- X 3 S g (0-0) or (1-0) Band at 1121 A
n+ State II State
q r
1 2 ° P 1 2
nP
13 p° 12
N Obs Cal Obs C al Obs Cal Obs Cal Obs Cal
1 (8 9 077.2) 8 9 0 77.1 A 8 9 0 8 7 .2 8 9 0 70.3
3 (8 3 .6 ) 8 3 .6 8 9 0 6 2 .8 62. 8 8 9 0 9 9 .2 9 9 .4 *89057. 7 89057. 9 70. 7
5 (9 0 .3 ) 9 0 .4 57. 7 57. 7 1 1 2 .4 1 1 2 .2 A 46. 9 7 1 .6
7 9 7 .1 9 7 .6
5 2 .9 5 3 .0 1 2 4 .7 1 2 5 .0 (3 5 .9 ) 3 6 .2
7 2 - 7
Not 7 4 .2 9
104. 3 105.3 * 4 8 .2 48. 7 138. 6 1 3 8 .6 2 6 .5
2 5 .9
1 1 1 1 2 .4 1 1 3 .4 4 4 .2 44. 9
A
15. 7 r e so lv e d 75. 9
13 122.3
1 2 1 .9 40. 9 41. 6 6 . 0 6 . 0 7 7 .5
15 1 3 1 .4 131.3 (3 9 .0 ) 3 8 .6
17 A
36. 5
VQ = 89071. 1 c m ^ V Q = 89070
, - 1
. 2 c m
B ' = 1 .4 8 6
V
C
B ' = 1.486
V
C
d ' = 1 x 1 0
V
- D
D ' = 5. 0 X
V
1 0
A See T able 1 - a (F 3 )
( ) See Table 1 - a (F 3 )
* See T able 1 - a (F 3 ) ► £
55
r e s u lts lis t e d in the ta b le s a g r e e w e ll w ith what is d e s c r ib e d above
3
e x c ep t in the n ^ subband w h ich is r e la tiv e ly w eak am ong the th ree
subbands and w h er e not enough data a r e obtainable to evalu ate the
3 +
rotation al co n sta n ts for the sta te . F r o m the sp littin g s o b se r v e d
for the subbands, one could d istin g u ish the upper state of the h ig h e st
3 3
subband (or the lo w e s t subband) bein g n £ or IT q and thus d e ter m in e
the tr ip le t bein g n o r m a l or in v e rte d . B a s e d on th is it is conclu ded
3
that the upper sta te is a n o r m a l n .
u
Due to the overlap p in g of the other bands the shading of the
ro tation al lin e s could not be d e te r m in e d , thus one could not judge
fr o m the shading to d e te r m in e the upper state being n o r m a l or in
v e r te d a s w as done in the c a s e of the band at 1165 A.
The p o s s ib le v ib ra tio n a l quantum nu m b er of the upper sta te is
e ith e r 0 or 1. F o r v' = 0, n* is 3 .6 5 , and v' = 1, n* would be 3 .3 0 .
E ith er one of the n* v a lu e s is r e a so n a b le for a 4pa e le c tr o n . S in ce
u
no other m e m b e r of the v ib r a tio n a l p r o g r e s s io n h as b een o b se r v e d , it
is not c e r ta in the lik elih o o d of w h ich vib ra tio n a l quantum num ber is
m o r e than the oth er.
56
3 -
9 . (rr 2p) 4f C o m p le x - X E (0 -0 ) B ands in the R eg io n fr o m 1106
£ > § ! ________________________________________
to 1103 A;
The sp e c tr u m of th is r e g io n (F ig u re 7) a p p ea rs quite d ifferen t
fr o m a ll the other bands a n a ly zed in the r e g io n of in te r e s t. The r o ta
tion al lin e s a r e v e r y sh arp and c lo s e ly sp a ced , a s o b se r v e d in the
c a s e of nf c o m p le x e s of NO, w h ich is the only other o b se r v e d nf c o m -
19
p le x e s. B e c a u s e of the u nu sual ro tation al str u c tu r e , the NO c o m
p le x e s w e r e a n a ly zed w ith c o m p le te ly d iffe r en t than con ven tion al
m eth o d s w ith the aid of low te m p e r a tu r e sp e c tr u m and iso to p e N ^ O ^
sp e c tr u m , w h ich r e m o v e d m o s t of the other overlap p in g band s.
B e c a u s e of the n e a r ly n on p en etratin g c h a r a c te r is tic of R ydberg f e l e c
tron o r b ita ls , the m o le c u la r sta te is p r a c tic a lly f r e e fr o m p r e d is
so c ia tio n w h ich is one of the c a u s e s of d iffu s e n e s s of the sp e c tr u m .
A ls o due to th is p r o p e r ty of non p en etratin g the m o le c u la r state
b e c o m e s v e r y s im ila r to a to m ic c a se ; and the coupling b e tw e e n the
o rb ital angular m o m e n tu m J L and the fig u r e a x is of the m o le c u le
b e c o m e s v e r y w ea k or c o m p le te ly d ecou p led . T h us, the m o le c u la r
s ta te s that defined for H und's c a s e (a) or (b) a r e no lo n g er v a lid for
s ta te s re su ltin g fr o m nf e le c tr o n s . A t the sa m e tim e , the m o m en tu m
j I for the f e le c tr o n then c o u p le s w ith the n u c le a r ro ta tio n a l a x is , and
the Hund1 s couplin g c a s e (d) is r e a liz e d .
/ / \
\ l /
Y
J J 17
3 -
F ig u r e 7. 4f C om p lex - X E at 1103 A
s O l
58
F o r the p r e s e n t 4f c o m p le x bands, due to the la c k of h igh -
18
r e so lu tio n low tem p e r a tu re sp e c tr u m , and iso to p e 0 ^ sp e c tr u m , and
a ls o the n e c e s s a r y th e o r e tic a l in form ation , it is not p o s s ib le , at the
m o m e n t to p e r fo r m the sa m e a n a ly s is a s done in the NO c a s e .
T h e r e fo r e , con ven tion al m ethod v/as s till u sed . In addition, 0 d o es
c *
1 + +
not have the s y m m e tr ic c o r e ( E ) as NO sin c e the ground state of O
2
is n (c a se a). It w as hoped that the Hund's c a s e s (a) and (b) would
§
s till b e m ean in gfu l for the p r e s e n t f c o m p le x . H o w ev er, the r e s u lts
w e r e rath er disappointing sin c e one w a s not ab le to identify the upper
sta te s in te r m s of c a s e (a) or (b) at a ll. N e v e r th e le s s , w ith the help
of the low tem p e r a tu re sp e c tr u m (photographed in our la b o r a to r y at
USC w ith lo w e r reso lu tio n ) one h as p ick ed out the b r a n c h e s in the
s o
fo r m s of P , Q, R, R , and P , and the m o le c u la r co n sta n ts a r e e v a l
uated a c c o rd in g ly . T h ey a r e lis t e d in T ab le 9 -a through h. T h e se
b ra n c h e s a r e g e n e r a lly sh o r te r and l e s s c e r ta in than the other bands
w ith np e le c tr o n s , sin ce in so m e c a s e s a lte r n a tiv e s w e r e lik e ly a s w e ll
b e c a u s e of the n u m ero u s rotation al lin e s o b se r v e d and the overlapp ing
of the bands.
A F o r tr a it d ia g r a m w a s plotted for a ll the o b se r v e d fo r m s of
b r a n c h e s in F ig u r e 7. It a p p ea rs that th ere a r e two c o n v e r g en ce
2 2
lim it s corresp o n d in g to the X n , and X II - sin c e th ere a r e two
g£ g3/2
r e la tiv e ly strong groups of b r a n c h e s o b s e r v e d at d ista n c e about sa m e
a s b etw een th e se two s ta te s . E a c h of the two groups a r e c o n sistin g
of b ra n c h e s w ith th eir h ead s v e r y c lo s e to ea c h oth er, but th e re a re
s o m e w eak b r a n c h e s lyin g in b e tw e e n th e se two g ro u p s. A ll the n*
v a lu e s ca lcu la ted b e sid e the p r e s e n t bands a r e using the s e r i e s lim it
at the m id d le p o sitio n of the above two s ta t e s ,^ sin c e it is not c le a r
w h ich of the two sta te s that th ey a r e con vergin g to. To c a lc u la te the
n* v a lu e s for the p r e s e n t nf c o m p le x , s e r i e s lim it s co rresp o n d in g to
the actu al p o sitio n s of th eir two s ta te s a r e u se d depending on w h ich
grou p s of b r a n c h e s they appear to b e . The b ra n c h e s in b e tw e e n a re
s till ca lc u la ted w ith the m id d le v a lu e for th eir n * 's . The n* v a lu e s
thus ca lc u la ted y ield v a lu e s ranging fr o m 4. 00 to 4. 03. Yam aw aki
24
and Ogawa o b se r v e d the v' = 1 and v' = 2 m e m b e r s of the 4f c o m
p lex . T h ese n* v a lu e s a g r e e r e a so n a b ly w ith th o se obtained by th em
for the higher two m e m b e r s (ranging fr o m 3. 99 to 4. 01).
(a) B r a n c h e s at 1106 A (T able 9 -a):
T h er e a r e four b ran ch fo r m s o b se r v e d , Q, ° P , R, and P .
A m ong th em , Q fo r m b ran ch is s tr o n g e s t in in te n sity . ° P fo r m
b ranch sh ow s up c le a r ly at the lo n g er w a v elen g th end of th is region ,
a p p ea rs to doublet. The R fo r m b ran ch is o b sc u r e d b y the adjacen t
strong group of b r a n c h e s at the sh o r te r w a v elen gth sid e, and is not
evid en t. S in ce this and a ll the other bands o b se r v e d w ith upper state
of 4f c o m p le x a r e lo c a te d at lo w e s t p o sitio n in the e n e r g y s c a le for 4f
60
T A B L E 9 - a
N
4f C o m p lex - X 3E " (0 -0 ) Band at 1106 A
_____________________S
R fo r m P fo r m Q fo r m P fo r m
7
9
11
13
15
9 0 4 3 7 .7
4 4 6 .5 9 0 4 2 3 .4
45 6 . 9
466. 7
476. 9
4 2 0 . 9
4 1 9 .3
417. 2
4 8 9 .0 (4 1 6 .6 )
41 7 . 2
9 0 4 2 5 .5
(428. 0 )
430. 8
43 5 . 6
442. 5
451. 0
462. 2
9 0 4 1 1 .4
0 9 .5
4 0 2 . 1
400. 5
393. 9
91. 6
387. 5
8 5 .4
382. 8
80. 1
380.. 1
7 7 .4
(379. 1)
Vq = 90430 c m
B ' = 1. 582
v
D ' > 0
v
- 1
Vq = 90425. 1 c m
B ' = 1. 567
v
D ' < 0
v
- 1
( ) S ee T ab le 1 - a (F 3 )
61
e le c tr o n s , it is thus c e r ta in that the v ib r a tio n a l quantum nu m b er of
a ll th e se bands is z e r o (v 1 = 0). The n* c a lc u la ted u sing lo w e r lim it
(« 97265 c m y ie ld s a v a lu e of 4. 00, ind icatin g a quantum d e fe c t of
0 , ty p ica l v a lu e fo r nf e le c tr o n s .
(b) B r a n c h e s at 1105 A (T able 9 -b):
T h e s e a r e the s tr o n g e s t b r a n c h e s o b se r v e d in th is 4f c o m p le x
r e g io n . H o w ev er, the in te n sity d e c r e a s e s v e r y ra p id ly in the higher
s o
m e m b e r s . T h er e a r e R, P , R, Q, and P fo r m of b r a n c h e s. Only
a few m e m b e r s fo r R and P fo r m b r a n c h e s a r e o b se r v e d , n* valu e is
4. 01, u sin g the lo w e r lim it.
(c) B r a n c h e s at 1104 A (T able 9 -c):
T h e s e a r e r e la tiv e ly w ea k b r a n c h e s. T h ere a r e a ls o fiv e fo r m s
S O s
of b r a n c h e s (R, P , R, Q, and P) o b se r v e d . A m ong th em , R is the
s tr o n g e s t and R a p p e a r s to be doublet. The two rotation al co n sta n ts
obtained a r e quite d ifferen t a s show n in the tab le, n* v a lu e is 4. 01
u sin g the m id d le v a lu e of s e r i e s lim it.
(d) W eak B r a n c h e s at 1104 A (T able 9 -d);
The b r a n c h e s (R and P fo r m s ) a r e p ick ed out fr o m the head
p o sitio n s of the b r a n c h e s show n in the low tem p e r a tu re sp e c tr u m .
T hey a r e not evid en t in the r o o m tem p e r a tu re sp e c tr u m . Only th ree
m e m b e r s of ea c h b r a n c h e s a r e o b se r v e d . E a ch of th em c o n s is ts of
T A B L E 9 - b
4f C o m p lex - S" (0 - 0 )
S
Band at 1105 A
N
g
R fr o m Q fo r m ° P fo r m R fo r m P fo r m
1 9 0 4 5 9 .7
(9 0 4 4 5 .5 ) - 9 0 4 4 6 .5
3 4 7 3 .3 447. 5 9 0 4 2 9 .1 * 456. 9 9 0 4 3 2 .2
5 486. 6 449. 5 4 1 9 .3 466. 7 430. 8
7 5 0 1 .4 (451. 9) 409. 5 4 7 5 .3 429. 1
9
5 1 6 .2 454. 5 * 400. 5 (4 2 6 .4 )
1 1 531. 0 456. 9 391. 6
13 459. 7 382. 6
15 374. 0
- 1
- 1
Vq = 90445. 3 c m
1 1
o
>
90440 c m
B ' = 1 .5 7 2
d W
V
B ' «
V
1 . 6
* S ee T ab le 1 - a (F 3 )
( ) S e e T able 1 - a(F )
63
T A B L E 9 - c
4f C o m p le x - X £ (0-0) Band at 1104 A
N R fo r m P fo r m SR fo r m Q fo r m
1 9 0 5 4 0 .1
38. 3
-9 0 5 4 8 . 9
3 * 548. 9
46. 6
(9 0 5 2 5 .7 ) 561. 3 (9 0 5 3 4 .5 )
5 5 5 9 .2
57. 2
(5 2 3 .0 ) 574. 1 (5 3 5 .4 )
7 5 7 1 .2
6 9 . 0
(5 2 1 .8 ) 587. 5 (536. 7)
9
585. 8 (522. 3) * 600. 7 (538. 6 )
1 1 (5 2 5 .4 ) 614. 2 5 4 0 .4
13 * 5 4 2 .1
VQ = 90533
- 1
c m
V 0
= 9 0 5 3 3 .9
B ' = 1. 65
V
B '
V
D '
V
= 1 .4 9
« i o “5
(4 8 7 .4 )
479. 0
(467. 9)
- 1
* S ee T able 1 - a(F^)
( ) S e e T ab le 1 - a (F 3 )
T A B L E 9 - d
4f C o m p lex - X 3£ " (0-0) Band at 1104A
§
N R fo r m P fo r m
1 9 0 5 7 6 .4
4. 1
3 582. 7 9 0 5 6 1 .3
0 .3 5 9 .2
5 5 8 9 .5 (5 5 6 .6 )
7 .5 4 .5
7 5 5 2 .8
1.2
Vq ~ 90567 c m
B 1. 5
v
- 1
( ) S ee T able 1 - a (F 3 )
65
doublet com p on en ts w ith about 2 c m ^ d iffe r e n c e in en erg y , n*,
u sing the m id d le v a lu e of s e r i e s lim it, c a lc u la ted is 4 . 02.
(e) B r a n c h e s 1103 A (T able 9 -e):
T h er e a r e four b r a n c h e s (R, P , Q, and ° P fo r m s ) o b se r v ed .
R fo r m ap p ea rs to be doublet. A s in (d), th e se a r e a ls o picked out
fr o m the low tem p e r a tu re sp e c tr u m . Two rotation al con stan ts a r e
obtained. The n* is 4 .0 0 u sin g the h igh er s e r i e s lim it (= 97460 c m *).
(f) S tronger B r a n c h e s at 1103 A (T able 9 -f):
T h e s e two b ra n c h e s (R and P fo r m s ) a r e strong and a lso appear
to be doublet, but v e r y sh ort. O nly th r e e m e m b e r s a r e o b se r v ed for
ea ch . The b ranch heads show v e r y d is tin c tiv e ly in the low te m p e r a
ture sp e c tr u m , n* is 4. 0 u sing the h igh er lim it.
(g) A nother group of B r a n c h e s at 1103 A (T able 9 -g):
s o
T h er e a r e fiv e b r a n c h e s ( R, Q, P , R and P fo r m s) o b se r v ed .
The B 1 v a lu e s obtained a re quite d ifferen t. Due to p r o b le m of o v e r
lapping, the a s s ig n m e n t of the b r a n c h e s a re not d efin ite, n* is 4. 01
u sing the h igh er lim it.
(h) B r a n c h e s at 1102 A (T able 9 - h ) :
s o
T h ese a r e sh ort and v e r y d iffu se b r a n c h e s ( R, Q, and P
fo r m s ), som ew h at d ifferen t fr o m the other bands in the 4f c o m p le x
66
T A B L E 9 - e
4f C om p lex - X 3S ” (0-0) Band at 1103 A
N R fo r m P fo r m Q fo r m P fo r m
1
3
5
9
11
90607. 2
05. 2
614. 2
12. 7
623. 9
2 1 .4
634. 6
3 3 .2
9 0 592 . 6
(588. 3)
(586. 5)
* 5 8 5 .8
90601.8
6 0 2 .2 9 0 5 8 7 .5
603. 7
6 0 5 .2
6 0 7 .2
5 7 6 .4
566. 6
555. 9
546. 6
VQ ^ 9 0 6 0 0 c m
B ' « 1 .6
v
D ' < 0
v
- 1
Vq = 9 0 6 0 1 . 6 c m
B 1 = 1. 509
v
D ' > 0
v
* See T able 1 - a (F 3 )
T A B L E 9 - f
4f C o m p lex - X^£ (0-0) Band at 1103 A
N R fo r m P fo r m
1 9 0 6 3 7 .8
39. 8
3 646. 9 9 0 6 2 3 .9
4 9 .0 2 6 .3
5 6 5 6 .4 6 2 1 .4
5 8 .3 2 3 .9
7 6 1 9 .5
2 1 .4
VQ ~ 90631 c m
B 1. 6
v
-1
68
T A B L E 9 - g
P fo r m
9 0 6 5 4 .0
53. 1
* 6 4 9 .0
46. 9
645. 0
43. 2
9
703. 8
1. 5
646. 9
45. 0
600. 7
599. 1
1 1 710. 9
9 .3
643. 0
41. 5
585. 8
13 718. 5
16. 3
639. 8
37. 8
15 634. 6
N
4f C o m p lex - X (0-0) Band at 1103A
SR fo r m Q fo r m ° P fo r m R fo r m
3
5
9 0 6 6 4 .3
62. 2
(6 7 3 .5 )
71. 5
6 8 6 . 3
695. 8
93. 9
-9 0 6 4 9 . 0
4 6. 9
646. 9
45. 0
649. 0
46. 9
-9 0 6 2 3 .9
2 1 .4
609. 7
7 .2
* 9 0 6 6 9 .3
67. 3
674. 8
682. 8
80. 7
Vq = 9 0 6 5 0 .3 c m ^ Vq w 90662 c m ^
B ' « 1 .3 9 B ' w 1 .5 5
V -4 V
D ' » 10
v
* See T able 1 - ^(F^)
( ) See T able 1 - a (F 3 )
T A B L E 9 - h
3 -
4f C o m p lex - X S (0-0) B and at 1102 A
6
N SR fo r m Q fo r m ° P fo r m
1 9 0 6 8 6 .5 * 9 0 6 6 9 .3
3 6 9 9 .5 6 7 1 .5
5 (6 7 3 .6 ) 9 0 6 4 6 .9
7 6 3 6 .6
Vq w 9 0 6 6 8 c m *
B ' « 1. 65
* See T able 1 - a (F 3 )
( ) S ee T ab le 1 - a (F 3 )
r e g io n . But c lo s e ex a m in a tio n sh ow s e a c h d iffu se lin e c o n s is t s of
m a n y fin e lin e s , thus a p p ea rs to b e d iffu se . The rotation al co n sta n ts
i s r e la t iv e ly la r g e (1 .6 5 c m ^). The n* y ie ld s a v a lu e of 4 .0 3 , using
the h igh er s e r i e s lim it.
71
10. (T T 2p)(4pTT ) 3 I]“ - X 3s " (1-0) Band at 1102 &
g r u' u_g _________________________
T h is is a strong band but w ith d iffu se rotation al lin e s (F ig u re
8 ). It is lo ca te d n ear the group of bands of 4f co m p le x . The r e a so n s
that th is band is not lik e ly p art of th em are: (1 ) the rotation al lin e s
a r e d iffu se and (2 ) the str u c tu r e of the band is d ifferen t, it r e s e m b le s
th o se bands w ith upper sta te s of Hund's coupling c a s e (a) or (b). H ow
e v e r , only sh ort b r a n c h e s a r e o b se r v e d due to the overlapp ing of the
adjacen t band at its sh o r te r w a v e le n g th sid e and a ls o the rapid d e
c r e a s e of the in te n sity . T h ere is no Q b ranch o b se r v e d , but two R
b r a n c h e s and two P b r a n c h e s . The m u ltip le lin e ap p earan ce of the
3 _
sp e c tr u m su g g e stin g that the upper state is v e r y lik e ly a E state
rath er than a tra n sitio n (se e A ppendix). T h ere a re four b r a n c h e s
o b se r v e d . It w a s u n s u c c e s s fu l to id en tify th em a s to w h ich spin c o m
ponent ea c h b e lo n g s. T h ey a r e ju st la b e le d a s R , R, , and P , P
a b a b
only. The P b r a n c h e s a r e not r e s o lv e d . The R^ and P^ m a y be c o n
sistin g of two o v erla p p ed m a in b r a n c h e s r e s p e c t iv e ly , sin c e the r o ta
tional lin e s of R^ b ran ch a r e m o r e d iffu se . T hey a r e lis t e d in T able
10. T h er e a r e two s e ts of m o le c u la r co n sta n ts obtained, one for ea ch
pair of b r a n c h e s (R and P ). The v a lu e s (1. 70, 1. 6 6 c m *) are
3 -
m u ch h igh er than o b se r v e d (3pTT^) E u band at 1154 A, but v e r y c lo s e
2
to that of the s e r i e s lim it X n . T h is show s that the p r e s e n t upper
S
3 _
state is not being p ertu rb ed , although the PpT^) £ u state ap p ea rs to
72
3i ;
+
7
T - -i— i Rb
-T 1 Re
r b
Pa
m
n
J 1 sR2 i+ sR 32 - I i I i i i i
3 15 1
^ - i - L U Q ,+ q 3
— I Q ,
R - I L
11
(b) C a )
j i i
15
3 1 1
J !_ J ! __! __I_I
9 1
■.l.u .!■!»_
3 15
Q
( C )
11
j I I
11
J L
Q
15
_ i_
J i I » .i.ll
1 1
7 1
F ig u r e 8 . 3 £ - , & 3 S + - X 3 E“ B ands at 1102 and 1101 A,
_ and W eak B ands (a), (b), (c) at 1098 and 1095 A
73
T A B L E 10
(rr 2p)(4pn ) 3E _ - X 3 e ' (1 -0 ) Band at 1102 A
g u u_g ________________________
N R P
R.
P
a a b b
1 9 0 7 5 4 .4 9 0 7 5 6 .6
3 763. 6 (90740. 1) 7 6 6 .4 (9 0 7 4 2 .2 )
5 775. 9 (737. 7) 7 7 8 .2 (7 4 0 .5 )
7 ’ 790. 3 (738. 5) 792. 8 (7 4 1 .8 )
9 (7 4 1 .4 )
(743. 9)
1 1
-
f V0 «
90747 c m " 1
t v o “
90749 c m 1
_ i
B « 1 . 6 6 B w 1. 70
V V
D ' < 0 D ' < 0
V V
( ) See T ab le 1 - a (F 3 )
I'Vq' s a r e d efin ed a s the h eigh ts of the F^ or (upper spin
su b sta te s fo r R^, P^; and R^, P , r e s p e c tiv e ly ) of the n ' = 0
sta te, r e s p e c t iv e ly .
74
be g r e a tly p ertu rb ed (Section 6 ). T he v a lu e s a r e not obtained, but
rough e stim a tio n sh ow s th ey a r e p o s s ib ly n eg a tiv e v a lu e s. The v ib r a
tion al quantum num ber i s a s s u m e d to b e 1 , s in c e it y ie ld s the m o s t
lik e ly n* v a lu e (3. 60) fo r a p e le c tr o n .
75
11. W eak B ands fr o m 1098 to 1095 A:
T h e r e a r e th ree bands in this reg io n , w ith v e r y w eak but
m o s t ly sh arp rotation al lin e s . T h ey a r e o b se r v a b le only in the high
p r e s s u r e s p e c tr u m (F ig u re 8 ).
(a) T h is band is so m e w h a t d iffu se . The rotation al lin e s exh ib it u n r e
so lv e d w eak com p on en ts at th eir s id e s . Two d efin ite b r a n c h e s R and
P and a sh o rt Q b ran ch a r e o b s e r v e d . The P b ran ch is m u ch w ea k er
than the R b ran ch . T h ey a r e lis t e d in T ab le 1 1 -a togeth er w ith the
m o le c u la r c o n sta n ts. T he d ifferen t n* v a lu e s ca lcu la ted a r e 4. 20,
3 .6 8 , and 3 .3 2 for v 1 equal to 0, 1, and 2, r e s p e c t iv e ly . It is lik e ly
that the upper state of th is band being sta te, w h ich r e q u ir e s an
e x c ite d (npa^) e le c tr o n . F r o m the above n* v a lu e s , the p o s s ib le
v ib ra tio n a l quantum nu m b er is e ith e r 0 or 2. Since the valu e n* = 3 .6 8
s u g g e s ts a d or s e le c tr o n , w h ich r e s u lt s in a ^ IT sta te. T h is i s ,
&
although p o s s ib le , l e s s lik e ly .
(b) O nly a R b ra n ch and a P b r a n c h e s a r e o b se r v e d in this band
(T able 1 1 -b ). T h ey appear to be sin g le t. The upper state is v e r y
lik e ly a ;A a te, but the doub let com p on en ts for ea ch b ranch a r e not
o b s e r v e d , a s in the c a s e of the band of S ectio n 7. The v ib ra tio n a l
quantum num ber could be e ith e r 0 or 2, w ith n* v a lu e of 4. 21 and
T A B L E 11 - a
W eak B ands fr o m 1095 to 1198 A
N R P
1 9 1 1 0 6 . 3
3 1 1 2 . 8 9 1 0 9 2 . 1
5 120. 5 87. 5
7 128. 8 83. 1
9
138. 6 80. 7
1 1 148. 0 77. 8
13 1 5 9 .2 7 6 .3
15 172. 7 75. 9
17 77. 8
VQ = 9 1 0 9 9 .0
- 1
c m
B 1 = 1. 51
V
D ' < 0
V
Q
9 1 0 9 8 .3
A
100. 5
102. 5
104. 3
A S ee T ab le 1 - a(F^)
77
T A B L E 11 - b
W eak B ands fr o m 1095 to 1098 A
N R P
1 9 1 1 6 9 .7
3 177. 8 9 1 1 5 5 .5
5 1 8 7 .4 152. 1
7 198. 7 150. 0
9
2 1 1 . 0 150. 0
1 1 225. 0 (1 5 0 .7 )
13 153. 0
Vq = 9 1 1 6 2 .5 c m ^
B ' = 1. 604
v g
D ' « 10“
( ) See T ab le 1 - a (F 3 )
78
3 .3 2 , r e s p e c tiv e ly . S im ila r ly , v 1 = 1, w ith n* = 3 .6 9 in d ica tes a
(4drr ) e le c tr o n w h ich w ill r e s u lt in a l e s s lik e ly upper state of
6 8
(c) T h is band is lo ca te d at 1095 A. It is r e la tiv e ly w eak am ong the
g
th r ee band s. F o u r b r a n c h e s , R, P , R, and Q a re o b se r v ed . The
doub let com p on en ts of R b ran ch a r e a ls o o b se r v e d . T h ey a r e lis te d
in T able 11- c , w ith the m o le c u la r c o n sta n ts. The upper state is p r o b
ab ly a X nu sta te. The p o s s ib le vib ra tio n a l quantum num ber is a ls o 0
or 2 follow in g the sa m e c o n sid e r a tio n a s in band (a). The p o s s ib le n*
v a lu e s a r e 4 .2 5 and 3 .3 2 , r e s p e c tiv e ly .
79
T A B L E 11 - c
W eak B ands fr o m 1095 to 1098 A
N
R 1 R 2 P 1 P 2
SR Q
1 (91297. 8 ) 9 1 2 9 9 .4 9 0 3 0 9 . 6 90293. 6
3 306. 5 308. 5 9 1 2 8 3 .7 9 1 2 8 5 .0 324. 9 2 9 5 .3
5 316. 6 318. 8 (280. 6 ) (2 8 2 .6 ) * 3 4 2 .3 (2 9 9 .0 )
6 3 2 8 .4 330. 2 279. 2 2 8 1 .4 360. 7 304. 4
9 * 3 4 2 .3 3 4 4 .3 279. 2 2 8 1 .4 3 1 1 .5
1 1 357. 6 360. 7 2 8 1 .4 (2 8 4 .0 ) 3 2 1 .4
13
(285. 9)
*
330. 2
15
'fi
342. 3
VQ = 91290 . 0 c m ^ VQ = 91293
, - 1
. 1 c m
B 1 = 1. 640
V
B 1 = 1. 640
V
( ) See T able 1 - a (F 3 )
* S ee T ab le 1 - a (F 3 )
80
12. (T T 2p)(5pCT ) 3 n - X 3S (0 -0 ) Band at 1088 A:
______ g r c u u_______ g_________________________
T his band is v e r y s im ila r to the band at 1136 A (Section 1-b),
d iffu se and w ith th ree d istin c tiv e h ead s at d ista n c e about 1 0 0 c m *
3
apart, indicating an upper sta te of c lo s e to c a s e (a). H ow ever,
3
the in te n sity is c o n sid e r a b ly w e a k e r than a ll the o b se r v ed bands in
the r e g io n of in te r e s t. A n a ly s is w a s attem p ted for the lo w e r two sub-
3 3 3 -
bands ( Ilj, IIq - X £g)> s in c e the h ig h e st subband is not r e s o lv e d .
T he r e su lts a re lis t e d in T ab le 12. A ll the rotation al lin e s a r e lis te d
to the a c c u r a c y of c m ^'s a s in the other d iffu se band s. The m o le c
u lar con stan ts a re a p p roxim ate e stim a tio n s fr o m the a s s ig n e d
3 _
b r a n c h e s . It is found that the D' for the n state is n e g a tiv e , d e m -
v u
3 -
on stratin g a p o s s ib ility of a £u state lying lo w e r than the p r e s e n t
3
state p ertu rb in g, and r e su ltin g in a \ - t y p e doubling. F o r the IIq
3 +
sta te , only b r a n c h e s for the IIq state a r e lis te d , sin c e no approp riate
3 _
a s s ig n m e n ts for the b r a n c h e s of the IIq sta te w e r e obtained.
18
In the iso to p e 0_ sp e c tr u m , th is band is not o b se r v e d . B y
calcu latin g the n* v a lu e s using d iffe r en t v' v a lu e s , it is found that the
p o s s ib le vib ra tio n a l quantum n u m b e r s a r e 0, 2, and 3. F o r v 1 = 0,
n* is 4 .4 5 ; and v' = 2, n* is 3 .4 5 . T h ese n* v a lu e s a r e ap p rop riate
3
for 5p and 4p e le c tr o n s , r e s p e c t iv e ly . C o n sid erin g v' = 2, (4pa^) II
sta te , one s e e s that the band w ith upper sta te v' = 0 or 1 h a s b een ob
s e r v e d (band at 1121 A, S ection 8 ), but the n* v a lu e s for the two
T A B L E 12
(tt 2p)(5pg )
&
3n - X 3 S ’ (0-0) Band at 1088 A
u g
3 n i ( F 2 )
3n o(EV
n~
n l
n"
N
R _
2 1 PQ23 ‘ * 2 1
q p +q r ° p
21 23 23 R 1 P 1+PR13(+I>Q12 P 13
1 91846 91854 (91746) (91732)
3 52 91832 6 6 (91840) 91814 (57) (32) 91718
5 58 (26) 77 (40) 803 (6 8 ) (31) 706
7 6 6 2 1 (40) 792 (78) (31) 694
9 77 17
(2 9 ) 682
1 1 17
669
- 1 _ 1 - 1
Vq = 91838 c m Vq = 91838 c m Vq = 91732 c m
B » 1 .4 B ' « 1 .4 B 1 * 1 .4
V V V
D ' < 0
V
( ) Sam e a s in Table 1 - afF^)
82
d iffe r en t v ib r a tio n a l quantum n u m b e r s c a lc u la te d (3 .6 5 and 3 .3 0 ,
r e s p e c t iv e ly ) a r e d iffe r e n t fr o m the v a lu e 3 .4 5 obtained fo r the v' = 2
of the p r e s e n t upper s ta te , n* is 3. 15 w h ich i s not a co m m o n v a lu e
3
fo r p e le c tr o n s , but it is c o n s is te n t w ith th o se of the (3pa ) II sta te s
c u u
(v 1 = 0 and 1, S e c tio n 1). In addition, the rota tio n a l con stan t
- 1 3
(» 1 .4 c m ) is rou gh ly the s a m e a s that of the (3po^) II , v 1 = 0
3
sta te . H o w ev er, the band of upper state v' = 2, (3pCT^) is not ob
s e r v e d . C on seq u en tly, the v ib r a tio n a l quantum nu m b er of the p r e s e n t
upper sta te , being 2 or 3 is l e s s lik e ly than being z e r o , su g g e stin g an
3
upper sta te of (5po^) n .
83
C H A P T E R VI
SUM M ARY OF R E SU L T S AND CONCLUDING REM ARKS
A c o lle c tio n of all the r e s u lts of the o b se r v e d bands a r e lis te d
in T ab le 13 givin g the m o le c u la r c o n sta n ts, upper s ta te s , e le c tr o n ic
co n fig u r a tio n s, v ib ra tio n a l quantum n u m b e r s, and the e ffe c tiv e p r in
cip a l quantum n u m b e r s. T he e n e r g y d ia g r a m of the upper sta te s is
shown in F ig u r e 9.
It is evid en t that a n um ber of bands b e s id e the p erp lex in g 4f
c o m p le x a n a ly zed in the p r e s e n t w o rk have unusual c h a r a c te r is tic s
(m o le cu la r c o n sta n ts, and in te n s itie s ). A lthough the in te r p r e ta tio n s
a r e g iv en a fte r v e r y c a r e fu l c o n s id e r a tio n s, it is im p e r a tiv e that fu r
ther r e s e a r c h be done so that the p r e s e n t a rg u m en ts about th e se bands
could be c o n fir m e d or new c o n c lu sio n s could be draw n.
The future w ork should in clu d e the follow ing:
(1 ) h ig h -r e s o lu tio n s p e c tr u m in the sh o r te r w avelen gth ,
h e liu m continu um reg io n ,
(2 ) h ig h -r e s o lu tio n low te m p e r a tu r e sp e c tr u m in the p r e s e n t
and sh o r te r w a v elen g th h e liu m continuum r e g io n , and
18
(3) h ig h -r e s o lu tio n 0 s p e c tr u m fo r the p r e s e n t and the
c *
h e liu m continu um reg io n .
T h e s e sp e c tr a a r e n e c e s s a r y to in v e stig a te the s ta te s w h ich a r e higher
m e m b e r s of the p r e s e n t upper s ta te s and c lo s e r to the s e r i e s lim it
T A BL E 13
A b sorp tion B ands A n alyzed in the R egion fr o m 1085 to 1165 A
VQ(cm )
E le c tr o n ic
B '(cm D ^ (cm *)
Band
X(A)
Upper State Configuration
i
V n* R em a rk s
1 - a 1162 85902.5
2. 8
3
1.352
1.352
2.5 x
4 .7 x
10_6
10 6
85994.6
86085.0
2 1
n
u
( t t 2p)(3pa )
o ^
0 3. 11 1.398
1.434
6 x
1. 1 X
10
10-5
1136
\ )
1 -b
87986
88087
3ni
3n3 J
3n
u
(ng2p)(3pau) 1 3. 13 1. 52
1. 55
/V
10-4
diffuse
2 -a
1152 86841. 1
1.7
n+
n
1
n
u
(n 2p)(4pa )
O
0 3. 23
1.615
1. 611
6. 0 X
1.4 X
io:s
10
strong
& sharp
2 -b
1125
88889.0
88889.0
n+
i f
1 u
u
( t t 2p)(4pa )
6 \1
1 3. 25
1. 546
1.599
6 x
1.4 X
io: 5 5
10
diffuse
3 -a
1148 87121
124
F i
F 3
V
u
(tt 2p)(4prr )
O
0 3. 27
1. 712
1. 683
diffuse
& w eak
3-b 1125 88944
3 e +
u
(T T g 2p)(4pTTu ) 1 3.27 1. 672 5 X 10-5 strong
oo
T A B L E 13 - Continued
B and \(A )
VQ( c m )
U p p er S tate
E le c t r o n ic
C o n fig u ra tio n
i
V n :' :
B ' (c m
V
D 1 (c m *)
V R e m a r k s
3 - c 1101 90805
V
u
(T T 2p)(4pTT )
©
2 3 . 2 7 1. 615 ~ i o - 5
stro n g
b ut d iffu s e
4 - a 1144 8 7 3 7 0 .2 y
u
(7T g 2p)(4pTTu ) 0 3. 32 1. 701 1 .2 X 1 0 “5
4 -b 1120 8 9 2 6 6 .3
y
u
(T T g 2p)(4pnu ) 1 3 .3 2 1 .6 9 8 4 . 2 X i o - 5
5 1155 8 6 6 5 3 .7 y
u
(T T 2p)(3pTT )
O ^
6 2 . 2 8 1. 517 1 .5 x i o - 5 a s y s t e m
6 1154 8 6 6 7 5 .5
3 -
E
u
(ng 2p)(3pnu ) 0 or 1
3. 20
2. 96
1 .5 3 8 3. 6 x 1 0 “5
7 1153 867 2 8 . 7
1 -
E
u
(t t 2p)(3pn )
o
0 or 1
3 .2 1
2 . 9 7
1. 589 8 .4 x i o - 5 str o n g
8
1121 8 9 0 7 0 .2
71. 2
8 9 1 6 1 .6
8 9 2 5 7 .3
8 9 2 5 7 .3
'"o+ 3 n ° |
0 3 U
3 n I n i n
3 _ 1 u
n ? 3t t \
“ T T ■
\ 21
(T T g 2p )(4p au ) 0 or 1
3. 65
or
3. 30
1 .4 8 6
1 .4 8 6
1. 531
1 .5 8 7
1. 589
5 . 0 X
2. 0 X
3 X
2. 8 X
- I
10
i o - 5
i o - 5
i o - 5
3 +
n l
r o ta tio n a l
c o n sta n ts
n o t o b ta in a b le
9 - a
1106
9 0 4 2 5 .1
90430
4 f C o m p le x (n 2 p ) (4 f \u ) 0 4 . 00
1. 567
1. 582
< 0
> 0
oo
< ji
T A BL E 13 - Continued
„ » v J c m )
Band X(A) 0_______
9-b 1105
90440
445. 3
Upper State
4f C om plex
E le c tr o n ic
C onf igur ation
(T T 2p)4f\
g u
n-'
B 1 (cm D 1 (cm
v v R em ark s
4. 01
1. 6
1. 572 10
-4
9 - c 1104
90533
5 3 3 .9
4f C o m p le x (T T g 2p)4fXu 0 4 . 01
1. 65
1 .4 9 ~ 1 0 - 5
9 -d 1104 9 0 5 6 7 4 f C o m p le x (T T g 2p)4fXu 0 4 . 0 2 » 1 . 5
9 - e 1103
90600
601. 6
4 f C o m p le x (ng 2 p )4fXu 0 4 . 0
* 1. 6
1 .5 0 9
< 0
> 0
9 - f
1103 90631 4f C o m p le x (rrg 2 p )4 f\u 0 4 . 0 * 1 . 6
9 -g
1102
9 0 6 5 0 .3
662
4 f C o m p le x (ng 2p)4fXu 0 4 . 01
« 1 . 3 9
w l . 5 5
» 1 0 - 4
9 - h 1102 90668 4 f C o m p le x (rr 2p)4fX
g u
0 4 . 03 w l . 65
10 1102
90 7 4 7
90749
3 -
E
u
(T T g 2p)(4prru ) 1
3. 60
1. 66
1. 70
< 0
< 0
str o n g
but d iffu s e
1 1 -a 1098 91099
( l n u }
(n 2p)(5pa )
g u
o r (4pa^)
0 o r 2
4 . 2 0
or
3. 32
1. 51 < 0
W eak
Vint
11 -b 1098 91162
(1v
(T T 2p)(5pTT )
&
or (4pn )
u
0 or 2
4 .2 1
or
3. 32
1. 604 « i o ' 5
sh a rp
oo
o
TA BLE 13 - Continued
B and
\(A)
VQ(c m )
U p p er S tate
E le c tr o n ic
C o n fig u ra tio n V1 n*
B 1 (c m *) D 1 (c m
V V R e m a r k s
11 — c 1095
91290
29 3 . 1 <‘ nu>
(T T g 2p)(5pcju )
or (4pa^)
0 or 2
4 . 2 5
or
3 .3 2
1. 640
1 .6 4 0
91732
91838
X ,
3 - 1
Hi 5 I'z
» 1 .4
» 1 . 4 < 0
W eak
and
12 1088
91838
1 " , T
3 + 1[ u
n i
% '
(t t 2p )(5pa )
©
0 4 .4 5
« 1 .4
d iffu se
oo
88
10 cm
'T T a 'TIL. 3 z l
COMPLEX
9 . 5
5 --------
9 . 0
4 --------
— 3 3 --------
8 . 5
I
I
0 . 5
0 2x3X
F ig u r e 9. E n e r g y D ia g r a m of the Upper S ta tes of the
O b serv ed Bands
89
2
X II . A t the sa m e tim e sp e c tr a fr o m (2) and (3) could e lim in a te
S
s o m e of the overlap p in g b an d s, w h ich a r e p a r tic u la r ly n eed ed to be
able to an a ly ze the nf c o m p le x e s , b e s id e m o r e th e o r e tic a l in fo rm a tio n
about th em .
90
R E F E R E N C E S
1. K ru penie, P . H. , J. P h y s . C h em . R ef. D a ta , V ol. 1(2), (1972).
2. A lb e r ti, F . , R . A. A sh b y and A . E . D o u g la s, Can. J. P h y s . , 46,
337 (1968).
3. O gawa, M . and K. R . Y am aw ak i, Can. J. P h y s . , 4 7 , 1805 (1965).
4. P r i c e , W. C. and G. C o llin s, P h y s . R e v . , 4 8 , 718 (1935).
5. Tanaka, Y. , J. C h em . P h y s . , 2 0 , 1728 (1952).
6 . S c h a e ffe r , H. F . and F . E . H a r r is , J. C h em . P h y s. , 4 8 , 4946
(1965).
7. H e r z b e r g , G. , S p ectra of D ia to m ic M o le c u le s (D. Van N o stran d
C o ., I n c ., P r in c e to n , N. J. , 1950), p. 240,
8 . ---------, Op. c it. , p. 225.
9. ---------, Op. c i t . , p. 133.
10. E d len , B . , R ep . P r o g . P h y s . , 2 6 , 181 (1963).
11. B o y c e , J. C. and H. A . R ob in son , J. Opt. Soc. A m e r . , 2 6 , 133
(1936).
12. B a b co ck , H. D . and L. H e r z b e r g , A s tr o p h y s . J. , 108, 167 (1948).
13. Chang, H. C. and M. O gaw a, J. M ol. S p ectry . , 4 4 , 405 (1972).
14. Budo, A . , Z. P h y s . , 105, 579 (1937).
15. H e r z b e r g , G. , S p ectra of D ia to m ic M o le c u le s (D. Van N o stra n d
Co. , Inc. , P r in c e to n , N . J. , 1950), p. 226.
16. K ru penie, P . H. , Op. c i t . , p. 456.
17. H e r z b e r g , G. , Op. cit. , p. 281.
91
18. K o v a c s, I. , R otational S tru ctu re in the S p ectra of D ia to m ic
M o le c u le s (A m erican E ls e v ie r P u b lish in g C o. , Inc. , New
Y ork, N. Y. , 1969), p. 178.
19. Jungen, C. H. and E . M ie s c h e r , Can. J. P h y s . , 4 7 , 1769 (1969).
20. H e r z b e r g , G. , Op. C it. , p. 284.
21. K ru p en ie, Op. c it. , p. 4 5 6 -7 .
22. A su d d i, R . K. , C u rren t S c i. (B a n g a lo re), 160 (1968).
23. B h a le , G. L. and P . R . R ao, P r o c . Indian A c a d . S c ie n c e ,
S ectio n A , 67 (6 ), 3 5 0 -7 (1968).
24. Y am aw ak i, K. R . and M. O gawa, Internal T e c h n ic a l R ep. No.
U S C -V a c -U V -1 3 0 , U n iv e r sity of Southern C a lifo r n ia , Los
A n g e le s , C a lifo r n ia , S ep tem b er 1972.
25. H e r z b e r g , G. , Op. c it. , p. 285.
92
A P P E N D IX
In f ig u r e s 11 th ro u g h 18 a ll th e a n t is y m m e t r ic r o ta tio n a l l e v e l s a r e
o m itt e d , s i n c e n o t r a n s it io n i s a llo w e d to th o s e l e v e l s f r o m th e gro u n d
s ta te s y m m e t r i c l e v e l s .
18
16
14
12
10
8
6
4
2
0
■ 2
PAUL H . KRUPENIE
orp)+o+ rs°)
0 (° P )+ 0 ~ (z Po)-
a'A
— RKR
OTHER
0.8 1.2 1.6 2.0 2.4 2.8 3.2 3.6
INTERNUCLEAR DISTANCE (&)
Ki c i r e 2. P o te n tia l e n e rg y c u rv e* fo r O f , O * . a n d O }*
m a y b r o b t a i n e d f r o m i h p a u t h o r u p o n r r q u r a l .
i. Vet. 1, No. 2,1972
P o te n t ia l C u r v e s of 0 2 b y K ru p e n ie (S ee
94
3 Z “ Z — tU.
k/ y
6 -------------------------------------
A 7 — s
c
A
A c
II
O
2 -----r-
-4J
1
M ------ !
2 3
—1 ---------- T T 1 --------
--------s
n i . - .
T
1 1 1 s
R ,
F
N* J*
1
rJ I r
i
i
1
^ 3 1
9 ,
R
1
L t
r3
1
1
%
R
1
*1
A
1
r|
3
o
1
1
3
1
i
i
1 '
i
! ■
1
i
1
3 q
1 2
1
1
P 2
H
1
%
|l
|i
p 3 1
1
1
1
1 *
1
° q2 3
1
II
}t?
, [
1
1
1
1
1
5 6.
----l-i------
1 1
- 0 —1 -----+S
4------
1 3i
1 1 1
1
3 < -
--UJ______ . J—l---------------------+ s
i
1
' ■ n r ~ ..............................
1 2-------
r i
L |------------------------------------- +S
0
X 3 Z g
3 - 3 -
F ig u r e 11. E - X E T r a n sitio n D ia g r a m
95
(7) 6
(6 ) 5 .
(5) 4'
(4) 3<
(3) 2
N* J"
7.
7 8 6!
5 6 a
3 4"
TT2(F> >
a o,, Qj, o 3
o 3 o-
'32
R : 12 <32
32
32
Q.
32
32
^ 2
- s
- s
- s
+ s
+ s
+ s
1 2
0
+ S
x 3^
3 3 -
F ig u r e 12. ^>^3^ - ^ ^1rans^ * :’-on D ia g r a m
k7 = y
7-
T H (p2
96
- S
- S
- S
- S
- S
- S
- S
Q„ CL
N77 J77
3
1
R 2
I
I
'2 1
>23
j 3 .
Q.
23
°P
■ o i
3 ^ - . -
X 2
+ s
+ s
+ s
+ s
3 3 -
F ig u r e 13. II^F^) - X T r a n sitio n D ia g r a m
97
k' y
(6) 7 -
! 1 T 0 «Fi'
- s
(5) 6-
-S
(4) 5-
(3) 4-
(2) 3-
( 1) 2 -
1 •
0 -
- s
- s
■ — s
- s
- s
- s
P Q„
I P ,
P Q,'
I2|
Q,
Q,
% °Q,3
Q,-
n" j"
7 8 6 =
p R ,.
:+S
+S
1 -
1 2 -
=J=k
X 3Z '
J
+S
+s
3 3 -
F ig u r e 14. ^ ^ T r a n sitio n D ia g r a m
F ig u r e 15.
x 3z "
+ 3 -
£ - X £ T ra n sitio n D ia g ra m
u g
99
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Asset Metadata

Creator Chang, Han-Chuan Liu (author)

Core Title Rotational-Analysis Of High-Resolution Oxygen Molecule Absorption-Bands In The Region From 1085 To 1165 Angstroms

Contributor Digitized by ProQuest (provenance)

Degree Doctor of Philosophy

Degree Program physics

Publisher University of Southern California (original), University of Southern California. Libraries (digital)

Tag OAI-PMH Harvest,physics, molecular

Language English

Advisor Ogawa, Masaru (committee chair), Beaudet, Robert A. (committee member), Weissler, Gerhard L. (committee member)

Permanent Link (DOI) https://doi.org/10.25549/usctheses-c18-872563

Unique identifier UC11364369

Identifier 7400909.pdf (filename),usctheses-c18-872563 (legacy record id)

Legacy Identifier 7400909

Dmrecord 872563

Document Type Dissertation

Rights Chang, Han-Chuan Liu

Type texts

Source University of Southern California (contributing entity), University of Southern California Dissertations and Theses (collection)

Access Conditions The author retains rights to his/her dissertation, thesis or other graduate work according to U.S. copyright law. Electronic access is being provided by the USC Libraries in agreement with the au...

Repository Name University of Southern California Digital Library

Repository Location USC Digital Library, University of Southern California, University Park Campus, Los Angeles, California 90089, USA