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Atomic spark spectra of tin, Sn III, Sn IV, Sn V Wu, Chien-Ming 1967

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T H E A T O M I C S P A R K S P E C T R A O F T I N , S n III, S n I V , S n V . b y C H I E N - M I N G W U : B . S c . N a t i o n a l T a i w a n U n i v e r s i t y , 1962. A T H E S I S S U B M I T T E D I N P A R T I A L F U L F I L M E N T O F T H E R E Q U I R E M E N T S F O R T H E D E G R E E O F M A S T E R O F S C I E N C E In t h e D e p a r t m e n t of P H Y S I C S W e a c c e p t t h i s t h e s i s a s c o n f o r m i n g to t h e r e q u i r s t a n d a r d . T H E U N I V E R S I T Y O F B R I T I S H C O L U M B I A A P R I L , 1 9 6 7 . In p r e s e n t i n g t h i s t h e s i s i n p a r t i a l f u l f i l m e n t o f the r e q u i r e m e n t s f o r an a d v a n c e d d e g r e e a t the U n i v e r s i t y o f B r i t i s h C o l u m b i a , I a g r e e t h a t t h a L i b r a r y s h a l l make i t f r e e l y a v a i l a b l e f o r r e f e r e n c e and s t u d y , I f u r t h e r a g r e e t h a t p e r m i s s i o n f o r e x t e n s i v e c o p y i n g o f t h i s * t h e s i s f o r s c h o l a r l y p u r p o s e s may be g r a n t e d by the Head o f my D e p a r t m e n t o r by h i s r e p r e s e n t a t i v e s . I t i s u n d e r s t o o d t h a t c o p y i n g o r p u b l i c a t i o n o f t h i s t h e s i s f o r f i n a n c i a l g a i n s h a l l n o t be a l l o w e d w i t h o u t my w r i t t e n p e r m i s s i o n , . The U n i v e r s i t y o f B r i t i s h C o l u m b i a V a n c o u v e r 8 , Canada D e p a r t m e n t o f A B S T R A C T . The s p e c t r a of t i n have been photographed in the r e g i o n between 350A and 9000A using as s ources an e l e c t r o d e l e s s d i s c h a r g e and a condensed spark in helium. E x p o s u r e were taken by using a 3 meter n o r m a l incidence vacuum grating s p e c t r o g r a p h and a H i l g e r E-478 l a r g e interchangeable quartz and g l a s s p r i s m spectrograph. Among th i r t y four hundred and four l i n e s which were measured, two hundred and t h i r t y five l i n e s were c l a s s i f i e d in the s p e c t r a Sn I and Sn II on the b a s i s of square a r r a y s constructed by u s i n g the energy l e v e l s f r o m M r s . S i t t e r l y ' s " A t o m i c E n e r g y L e v e l s " , Volume 111 (1957). F i v e hundred and eleven l i n e s are h e r e i n c l a s s i f i e d in the s p e c t r a Sn III, o o Sn IV and Sn V. T A B L E O F C O N T E N T S . Page A B S T R A C T . . . . . . . . . . . . IV A C K N O W L E D G E M E N T S . . . . . . . . V I N T R O D U C T I O N . . . . . . . . 1 E X P E R I M E N T A L M E T H O D . . . 3 A N A L Y S I S O F R E S U L T S . . . . . . . . 6 The T e r m C l a s s i f i c a t i o n of Sn III . . . . . 6 a. E n e r g y L e v e l s O b s e r v e d « . . . . . 6 b. 5s5p, 5s6p, and 5s7p configurations . . 10 c. 5s5d, 5s6d, and 5s7d configurations . . 12 d. 5s4f and 5s5f configurations . . . . . 13 e. 5p4f configuration . . . . . 15 The T e r m C l a s s i f i c a t i o n of Sn IV . . 18 a. E n e r g y L e v e l s O b s e r v e d . . . . . 18 b. P o l a r i z a t i o n F o r m u l a . . . . . 20 c. ng. s e r i e s . . . . . . . . 21 The T e r m C l a s s i f i c a t i o n of Sn V . . . . . 22 a. E n e r g y L e v e l O b s e r v e d . . . ... 22 9 9 b. 4d 5 s and 4d 6s configurations . . 24 C O N C L U S I O N . . . . . . . . . . . 28 B I B L I O G R A P H Y . . . . . . . . . 29 i i L I S T O F T A B L E S . Table Page I Odd ^Energy L e v e l s of Sn III . . . . . 6 II E v e n E n e r g y L e v e l s of Sn III . . . . . 8 III C a l c u l a t e d and O b s e r v e d E n e r g y L e v e l s of 5s5p, 5s6p, and 5s7p of Sn III . . 12 IV C a l c u l a t e d and O b s e r v e d E n e r g y L e v e l s of 5s5d, 5s6d, and 5s7d of Sn III . . 12 V C a l c u l a t e d and O b s e r v e d E n e r g y L e v e l s of 5s4f and 5s5f of Sn III . . . . . 13 VI Complete f o r m u l a f o r pf in the p a i r -coupling approximation . . . . . 16 VII. O b s e r v e d and t h e o r e t i c a l s t r u c t u r e of 5p4f 16 VIII Odd E n e r g y L e v e l s of Sn IV . . . . . 18 IX E v e n E n e r g y L e v e l s of Sn IV . . 19 X Odd E n e r g y L e v e l s of Sn V . . . . . 22 . XI E v e n E n e r g y L e v e l s of Sn V . . 23 9 XII C a l c u l a t e d and O b s e r v e d L e v e l s of 4d 5s and 4d 6s of Sn V . . . . . 25 XIII T i n L i n e L i s t . . . . . . . . 29 L I S T O F F I G U R E S . F i g u r e P a g e 1. T h e c o n f i g u r a t i o n s p i n i n t e r m e d i a t e c o u p l i n g 14 2 . T h e c o n f i g u r a t i o n s d i n i n t e r m e d i a t e c o u p l i n g 14 3 . T h e c o n f i g u r a t i o n sf i n i n t e r m e d i a t e c o u p l i n g 15 4 . S t r u c t u r e of p f i n i n t e r m e d i a t e c o u p l i n g i n t h e p a i r - c o u p l i n g a p p r o x i m a t i o n . . . 17 5 . T h e c o n f i g u r a t i o n d ^ s i n i n t e r m e d i a t e c o u p l i n g 26 V A C K N O W L E D G E M E N T S . I w i s h to express my gratitude to Dr. A.M. C r o o k e r for his inte r e s t , a s s i s t a n c e , and encouragement during this r e s e a r c h . It is a ple a s u r e to acknowledge the t e c h n i c a l a s s i s t a n c e of Mr. A . J . F r a s e r , M r . J. L e e s , and Mr. W.J. M o r r i s o n . I N T R O D U C T I O N A recent review by Tousey (6) of spectroscopy i n the vacuum u l t r a v i o l e t pointed out the renewed int e r e s t i n the subject since 1945. T h i s i n t e r e s t contributed: much to the new field.where the extreme u l t r a v i o l e t is v e r y important. A n enormous amount of work is yet to be done i n the f i e l d , and many s p e c t r a have neither been completed nor investigated during the past twenty y e a r s . Some of these s p e c t r a which have not r e c e n t l y been ob s e r v e d are the second, t h i r d , and fourth spark s p e c t r a of t i n , Sn III, Sn IV, and Sn V. T h i s thesis w i l l p resent the r e s u l t s of a study of these s p e c t r a made during the past two y e a r s . White (7) published seventeen t e r m s and thirty-seven c l a s s i f i e d o o li n e s in the r e g i o n f r o m 1000A to 1500A in the f o u r t h spark s p e c t r u m of t i n , Sn V. Two important b a s i c t r a n s i t i o n l i n e s between even and odd low-lying l e v e l s , 4 d 9 5 s 3 D 3 - 4 d 9 5 p 3p£ ( )J =76793cm _ 1) and 4 d 9 5 s 3 D 1 - 4 d 9 5 p 3 P ° ( y =76794cm" 1) ) were ide n t i f i e d with the same o i strong 0 II line 1302.168A. )f =76795. 0cm" . The fact that the t r a n -s i t i o n which was being doubly c l a s s i f i e d was coincident with a strong 0 II line was not mentioned. In the tin line l i s t s p r esented below in Table XIII, the line O i l X. =1302.168A does not appear since the tin 2. l i n e s are m e a s u r e d with r e s p e c t to i m p u r i t y l i n e s of H, C, N, O and Si which occur strongly on my plate. The t e r m values of Sn III and Sn IV i n (5) were based on Shenstone's unpublished m a t e r i a l which was obtained using a condensed spark i n helium. The apparent inadequacy of White's data and the u n a v a i l a b i l i t y of Shenstone's l i s t s , as well as m o d e r n supporting work on cadmium, indium and antimony p r e s e n t l y being studied at U.B. C. made it mandatory to rephotograph, r e -m e a s u r e and r e i n t e r p r e t these s p e c t r a . The present work r e p r e s e n t s for the most p a r t an extrapolation of r e l a t i v e t e r m values i n the C d I, Ag I and A g II i s o e l e c t r o n i c sequence using the r e g u l a r and i r r e g u l a r doublet laws and the v a r i o u s extrapolation methods which a r e d e s c r i b e d by E d l e n (2). 3. E X P E R I M E N T A L M E T H O D . o Two sets of s p e c t r o g r a m s were taken i n the r e g i o n 350A to o 2400A, both using as source an e l e c t r o d e l e s s d i s c h a r g e . The es s e n t i a l of source tube, e l e c t r i c c i r c u i t and heating c i r c u i t were d e s c r i b e d in (8). A l l plates were I l f o r d type Q-2 pl a t e s . F r o m vapour p r e s s u r e data (9), the vapour p r e s s u r e of t i n can be approximated f r o m the e x p r e s s i o n log^Qp=A+BT~^", where A and B are coef f i c i e n t s c h a r a c t e r i s t i c of t i n . F r o m Table 1 of r e f e r e n c e (9) f p=10~ 4 mmHg T=1270°K p.=10"3 mmHg T=1380°K l o g i o 1 0 " 4 = A + B / 1 2 7 0 l o g 1 0 1 0 " 3 = A+B/1380 by solving these two simultaneous equations, we obtain A=8.55 B = -15932.73°K E x p o s u r e 1 was taken on a 3 meter n o r m a l incidence vacuum grating s p e c t r o g r a p h of l o c a l design (4) to cover the r e g i o n f r o m 350A. o to 244OA on the t h i r t y i n c h long plate holder holding one twelve and one eighteen inch plate. The oven surrounding the source tube was o heated to approximately 1200 C in o r d e r to provide enough vapour p r e s s u r e , 0.0053 mm Hg (9 ) i to initiate the d i s c h a r g e . The gate valve between the s l i t and the m a i n body of the sp e c t r o g r a p h was kept c l o s e d un t i l the p r e s s u r e within the spectrograph had dropped to 0. 2 m i c r o n Hg When the vapour p r e s s u r e r e a c h e d 0.005 mm Hg, the gate valve was open, and the p r e s s u r e i n the spectrograph r o s e to 0.5 m i c r o n , which held during the whole exposure time, 30 minutes. Developing time was two minutes, using Johnson A z o l developer diluted to 1 part i n 20 parts of water as recommended by the manufacturer. , Ex p o s u r e 2 and 3 were taken on the same set of plates in the same re g i o n as exposure 1. The temperature of the oven was f i r s t r a i s e d to o 1200 C only. E x p o s u r e 2 was taken for 30 minutes after the source di s c h a r g e had ru n for 30 minutes to eliminate i m p u r i t i e s . Since the intensity was so weak exposure 3 was taken by i n c r e a s i n g the oven temperature to approximately 1350°C i n order to provide more vapour p r e s s u r e , 0.0535 mm Hg (9). The source d i s c h a r g e then was ru n for 45 minutes under these conditions. Developing time was again two minutes using Johnson A z o l developer as d e s c r i b e d above. Another three sets of sp e c t r o g r a m s were taken on the H i l g e r i n t e r -changeable quartz and glas s p r i s m spectrograph a l l using as source a condensed spark i n helium. The es s e n t i a l s of the source tube, and e l e c t r i c c i r c u i t a re d e s c r i b e d i n (4). E x p o s u r e 4 was taken on a H i l g e r l a r g e quartz p r i s m spectrograph ° o set to cover the r e g i o n f r o m 2340A to 3100A on a ten i n c h I l f o r d type Q-2 plate. The source was ru n for 20 minutes i n p r e s s u r e of 6 c m Hg 5. of h e l i u m using a sl i t width of 8 m i c r o n s . A ten second i r o n a r c exposure was taken to provide standards by c l o s i n g the s l i t length diaphragm to 4 m i l l i m e t e r s . The plate was developed for two minutes in Johnson A z o l developer as d e s c r i b e d above. Exposure 5 was taken on a H i l g e r l a r g e quartz p r i s m spectrograph o o set to cover the r e g i o n f r o m 3100A to 7000A on a ten inch H P 3 plate. E x p o s u r e time and p r e s s u r e were the same as exposure 4 except another t h i r t y second neon discharge was taken to prov i d e the standards o to c o ver the r e g i o n above 5600A by c l o s i n g the s l i t length diaphragm to 6 m i l l i m e t e r s . The plate was developed for 5 minutes i n Kodak D -19 developer. E x p o s u r e 6 was taken on a H i l g e r l a r g e g l a s s p r i s m s p e c t r o g r a p h o o set to cover the r e g i o n f r o m 4500A to 9000A on a ten inch Kodak type 1-N plate. The source d i s c h a r g e was r u n f o r f o r t y minutes at a p r e s -sure of 6 c m Hg of helium. With the s l i t length diaphragm c l o s e d to 9 m i l l i m e t e r , a fo r t y second neon discharge was "taken to provide o standards to cover the region above 5600A. A fifteen second i r o n a r c exposure was taken to provide standards by c l o s i n g the sl i t length diaphragm to 3 m i l l i m e t e r s . The plate was developed for 8 minutes in Kodak D-19 developer. 6. A N A L Y S I S O F R E S U L T S .  The T e r m C l a s s i f i c a t i o n of Sn III. a. E n e r g y L e v e l s O bserved. Table I. Odd E n e r g y L e v e l s of Sn III.  C o n f i g u r a t i o n D e s i g . J L e v e l Interval 5s5p 3 P 0 53548.1 1648.6 1 55196.7 2 59229.0 lP 1 79911.9 5s6p 3 P 0 159940.3 1 160216.2 2 161439.1 *P 1 162725.9 5s4f 3 F 2 179308.0 3 179344.0 4 179442.3 1 F 3 179703.7 5p6s 3 P 0 188357.3 1 189013.7 2 192573.7 1 P 1 194513.3 4032.3 275.9 1222 .9 36.0 98.3 656.4 3560.0 Table I. cont. C o n f i g u r a t i o n D e s i g . J_ L e v e l Interval 70.2 309.2 43.8 5s7p 3 P 0 194954.7 1 195024.9 2 195334.1 1P 1 195500.6 5s5f 3 F 2 .204387.6 15.7 3 204403.3 4 204447.1 *F 3 204540.9 5p5d lT> 2 214154.5 3 D 1 215778.8 2 215857.1 3 216519.8 3 P 0 217057.5 1 216752.4 2 217620.8 ^ P 1 221524.8 3 F 2 216929-0 3 217372.4 4 221243.9 1F 3 221382.0 78. 3 662.7 •305.1 868.4 443.4 3871.5 T a b l e II. Co n f i g u r a t i o n 5s 5p 5p2 5s6s 5s5d 5s7s 5s6d 5s5g E v e n E n e r g y L e v e l s of Sn III J L e v e l D e s i g . 1 D D D 5s8s 0 0 1 2 2 0 1 0 1 2 3 2 1 0 1 2 3 2 3,4 5 4 1 0. 0 127309. 3 130120.7 134567.9 128206.0 15196.4 139638.9 143567.9 141321.8 141526.8 141838.6 154115.5 186671.2 187398.6 187918. 7 187998.3 188131.9 189690.2 206111.0 206135.2 206127.1 207960.2 Interval 2811.4 4447.2 205. 0 311.8 79. 6 133. 6 24. 2 Table II. cont. C o n f i g u r a t i o n 5s7d Desig. 1 5s9s L e v e l 1 208655.0 208702.6 208780.1 209259.5 219510.8 Interval 47. 6 77. 5 5p6p 5 P 4 f D 1 0 1 2 1 2 3 2 1 0 3 2 3 4 4 225859.0 226106.9 225952.4 226066.2 226834.3 227096.2 227031.0 227460.5 227800.3 227939.9 242088.7 242069.6 242112.6 242168.2 249365.6 -154.5 113.8 261.9 -65. 2 43. 0 156. 0 10. Table II. cont. C o n f i g u r a t i o n 5p4f Desig. D J L e v e l 3 248937.5 4 248947.9 5 249372.1 1 249404.9 2 249432.6 3 249224.9 2 249195.2 is 244418.cm Interval 10.4 424. 2 27. 2 -207.7 -1 T h e r e were t h i r t y - s i x odd and f o r t y - e i g h t even l e v e l s e s t a b l i s h e d i n this spectrum.. Two hundred and seventy six l i n e s have been c l a s -s i f i e d as Sn III t r a n s i t i o n s , b. 5s5p, 5s6p, and 5s7p configurations. If we denote by E the r e l a t i v e t e r m value, counted upward f r o m the ground state, and by E £ the value of the s e r i e s l i m i t c o n the same scale, the absolute t e r m value is defined as T = E,^ - E (1) F r o m Bohr's theory, T can be written as where £ = n - n*. We may express the R i t z f o r m u l a i n the f o l -lowing f o r m : £ = o<+ £ T (3) where and ^ a r e constants. T h i s is a r e m a r k a b l y good approxima-tion to o b s e r v e d unperturbed s e r i e s . It i s then v e r y convenient to start with an approximation value E ° ^ and the c o r r e s p o n d i n g values T ° and £ ° . The approximation r e l a t i o n follows f r o n v E q . (3) and the de f i n i t i o n of & : <>0+ A T =ofrfT (4) The c o r r e c t i o n value A T=E - E ^ can be determined f r o m three s e r i e s m embers (indices 1,2,3) by solving for £± T: (T1 - T 2 ) ( ^ 2 - 63) - ( T 2 - T 3 ) ( £ l - ^ 2 ) * T = 2 ( T X - T 2 ) ( n ^ / T 3 - n*/T 2) - ( T 2 - T 3 ) ( n * / T 2 - n f / T j ) ( 5 ) 5 s 5 p c . g . 67554 T ^ 178466 2. 352 ^ ° = 2. 648 5 s 6 p c . g . 161470 T 2 = 84550 n 2= 3.417 £ 2 =2.583 5 s 7 p c . g . 195262 T 3 = 50758 n 3= 4.411 £ 3 =2.589 Substituting these values into E q . (5), we obtain A T = -1602 c m " 1 2 1 -1 Therefore,:, i o n i z a t i o n potential (5s S Q) i s 244418 c m . T h i s method involves an i t e r a t i o n , which on the next a p p l i c a t i o n gave A T=25 c m " 1 The four energy l e v e l s of s X configurations are given by the r e l a t i o n s : ^3 I = F q - G f c - 1/2 ( £ + 1 ) J ^ j s + F q - 1 / 4 ^ 1 - J ( G A + l / 4 j A ( L ) 2 + 1/4 Jt( (6) _ 1+ ^ By introducing a coupling p a r a m e t e r vb = —, where 4G$_ , and e x p r e s s i n g the energy i n units of + (2 1 + l ) ^ x i 3 4 with 1/2 ( L j_ ) as z e r o l e v e l . We t r a n s f o r m Eq. (6) into 1. T A S (1) p. 271 s JL E ( L | - 1) = -1 E ( 3 L ^ + 1) = -1 + 2 f E ( X L i) .3 (7) C o n f i g u r a t i o n 5s5p V_ E ( L ^ ) Table III. C a l c u l a t e d and O b s e r v e d E n e r g y L e v e l s of  5s5p, 5s6p, and 5s7p of Sn III. Desig. J C a l . L e v e l Obs. L e v e l C a l . -Obs, 5s6p 5s7p 3 P 0 53548.3 53548. 1 0. 2 1 55149.3 55196.7 -47.4 2 59229. 1 59229.0 0. 1 1 p 1 79959.3 79911.9 47.4 3 P 0 159940.7. 159940.3 0.4 1 160221.4 160216.2 5.2 2 161439.0 161439. 1 -0. 1 1 p . 1 162720.8 162725.9 -5. 1 3 P 0 194956.8 194954.7 2. 1 1 195009.6 195024.9 -15.3 2 195333.6 195334. 1 -0.5 1P 1 195516.0 195500.6 15.4 c. . 5s5d, 5s6d, and 5s7d configurations. Table IV. C a l c u l a t e d and O b s e r v e d E n e r g y L e v e l s of 5s5d, 5s6d, and 5s7d of Sn III. Con f i g u r a t i o n D e s i g . J_ C a l . L e v e l Obs. L e v e l C a l . -Obs. 5s5d 3 D 1. 141322.1 141321.8 0. 3 Table IV. cont. C o n f i g u r a t i o n 5s5d D e s i g . 'D D J C a l . L e v e l Obs. L e v e l C al.-Obs. 141523.2 141526.8 -3.6 141836.4 141838.6 -2.2 5s6d >D 5s7d D 'D 2 1 2 3 2 1 154119.2 187919.0 187996.5 188131.3 189692.1 208656. 1 154115.5 187918.7 187998.3 199131.9 189690.2 208655.0 3. 7 0. 3 •1.8 •0. 6 1.9 1. 1 1 D 2 208699.1 208702.6 -3.5 3 • 208785'. 6 208780. 1 5.5 2 209263.2 209259.5 3.7 d. 5s4f and 5s5f configurations. T a b l e ! V . C a l c u l a t e d and O b s e r v e d E n e r g y L e v e l s of 5s4f and 5s5f of Sn III. Conf igur ation 5s4f Desig. J C a l . L e v e l Obs. L e v e l Cal.-Obs, 5s5f 2 179307.6 179308.0 -0.4 3 179352.0 179344.0 8.0 4 179442.8 179442.3 0.5 3 179695,8 179703.7 -7.9 2 204387.5 204387.6 -0.1 3 204406.0 204403.3 2.7 204446.7 204447.1 •0.4 3 204538;2 204540:9 -2:7 14. 15. e. 5p4f configuration. The complete f o r m u l a for pf in the p a i r - c o u p l i n g approximation was d e r i v e d b y ' E r i c k s s o n (3). The energy l e v e l s are shown in Table VI. 16, L i m i t J 1 1/2 1 1/2 1/2 1 1/2 1/2 1 1/2 Table VI. Complete f o r m u l a for pf i n the p a i r - c o u p l i n g  approximation. D e s i g . L K J G (4 1/2) 5,4 G (3 1/2) 4,3 F ( 3 l/2)'.4,3 D ( 2 1/2) 3,2 F (2.1/2)' 3, 2 D (1 1/4) 2, 1 Relati v e E n e r g y + 1/2 3p+ 5 F 2 \/4fr 5 F 2 t J(3/4/ f- 5F 2) 2+75F. 1/4 tp - 3 / 2 F 2 t ((3/4 Sf - 3 / 2 F 2 ) 2 +180F2 + 1/2 1+ 12F P 2 Table VII. O b s e r v e d and theoretical, s t r u c t u r e of 5p4f. Jobs. D e s i g . obs. E c a l . E , -E c a l . i (1 1/2) 2555 2707.8 152.8 (4 1/2) 2502 2502 0. 0 (2 1/2) 2345.3 2274.6 -70. 7 (3 1/2) 2076.2 2076.6 0.4 (3 1/2)' -4723.3 -4719.6 3.7 (2 1/2)' -4786.5 -4718.0 78.3 E = 246867, 2 c m - 1 X-f= 4710. 0 c m - 1 F 2 = 29.4 c m - 1 P a i r splitting -^ 50 c m -1 i It is seen f r o m F i g . 4 that the i n t e r a c t i o n energy has a d e c i s i v e influence on the t e r m s t r u c t u r e . The effect i s greater for K=2 1/2 than K=3 1/2. The magnitude approaches a ra t i o of 12;fc5' for F / approaching zero i n each of the two c a s e s . 0.00 0.05 0.10 F i g . 4. , Structure of pf in intermediate coupling i n the p a i r - c o u p l i n g approximation. The T e r m C l a s s i f i c a t i o n of Sn IV. a. E n e r g y L e v e l s O bserved. Table VIII. Odd E n e r g y L e v e l s of Sn IV. Co n f i g u r a t i o n Desig:. I : L e v e l 5p 2 P 1/2 69564.3 1 1/2 , 76072.8 6 P 2 P 1/2 197851.2 1 1/2 200031.3 4f 2 F 2 1/2 210318.2 3 1/2 210257.7 4 d 9 5 s ( 3 D ) 5 p 4 P 1/2 23,3153. 2 1 1/2 229110.0 2 1/2 223504.0 4 F 1 1/2 234038.7 2 1/2 229894. 1 3 1/2 229344.7 4 1/2 4 D 1/2 241051.3 1 1/2 237813.7 2 1/2 236270.4 3 1/2 236169.4 2 F 2 1/2 240881.6 3 1/2 243303.9 2 P 1/2 242980. 1 1 1/2 242715.4 Interval 6508.5 2180. 1 -60.5 -4043.2 -5606.0 -4144.6 -549.4 •3237. 6 •1643. 3 -101.0 2422.3 -264.7 19. Table VIII. cont. C o n f i g u r a t i o n 4 d 9 5 s ( 3 D ) 5 p 4 d 9 5 s ( 1 D ) 5 p 7p 5f 8p 6h 7h 8h D e s i g 2 ^ L e v e l 1 1/2 244708.6 2 1/2 246604.7 2 F 2 1/2 3 1/2 259875.4 2 D 1 1/2 260398.5 2 1/2 2 P 1/2 1 1/2 263718.5 2 P 1/2 250017.4 11/2 250838.5 2 F 2 1/2 254468.3 3 1/2 254447.9 2 P 1/2 274609.3 1 1/2 274716.2 2 H •.. 4 1/2,5 1/2 279786. 7 2 H 4 1/2,5 1/2 292714.4 2 H 4. 1/2,5 1/2 301114. 7 5s 5d Table IX. E v e n E n e r g y L e v e l s of Sn IV. J L e v e l . 1/2 Co n f i g u r a t i o n D e s i g 2„ 4 d 9 5 s 2 'D 'D 0. 0 1 1/2 165304.5 2 1/2 165410.8 1 1/2 177941. 1 Interval 1896.1 821. 1 -20.4 106.9 Interval 106. 3 •8707.5 20. Table IX. cont. C o n f i g u r a t i o n 4 d 9 5 s 2 6s D e s i 2 S g. J 2 1/2 1/2 L e v e l 169233.6 174140.1 6d 2 D 1 1/2 2 1/2 234798.9 235128.5 7 s 2 S 1/2 237617.5 |8s 2 s 1/2 268545.8 '5g. 2 G 3 1/2,4 1/2 258283.7 6g 2 G 3 1/2,4 1/2 279860.8 7g 2 G 3 1/2,4 1/2 292888.4 Interval Ionization potential ( 4 d ^ SQ) i s 328842.6 c m ^. In this s p e c t r u m there were t h i r t y - f o u r odd and thirtee n even energy l e v e l s e s t a b l i s h e d with one hundred and nineteen l i n e s c l a s -s i f i e d as Sn IV t r a n s i t i o n s , b. P o l a r i z a t i o n F o r m u l a . E l e c t r o n s such as nd, nf, ng, and nh have non-penetrating o r b i t s . The quantum defect & exhibits a s t r i k i n g r e g u l a r i t y i n its dependence on JL , which i s connected with the fact that for these s e r i e s S is d e t e r m i n e d almost e n t i r e l y by the p o l a r i z a t i o n of the atomic c o r e i n 2 the f i e l d of the outer e l e c t r o n . T h i s p o l a r i z a t i o n makes a c o n t r i -bution A p to the t e r m value T that may be written as ^ P = T - T H = A(Z)p(n, I) [ l + K(Z)q(n, JL ) J (8) 2. E q . (20.6) of Reference (z). W h e r e T is the absolute t e r m v a l u e , TV, is the c o r r e s p o n d i n g h y d r o -genie t e r m value c o r r e s p o n d i n g to the p r i n c i p a l q u a n t u m n u m b e r n . Tpj c a n be e x p r e s s e d as f o l l o w s : f>2 r ^ 2 ^ 2 \ T „ = ^i— 1 + j ( n - 3/4) (9) H - n * - [ n 7 ^ U + l / 2 J w h e r e o ^ i s the S o m m e r f e l d fine - s t r u c t u r e constant = -r and j Kc is the net c h a r g e of the c o r e . A ( Z ) and K ( Z ) a r e tabula ted i n T a b l e 19 of R e f e r e n c e (2). If we at l e a s t have three m e m b e r s of the T s e r i e s , E q . (8) c a n be u s e d f o r c a l c u l a t i n g the i o n i z a t i o n p o t e n t i a l . S i n c e q(n, ) is v e r y m u c h s m a l l e r than 1 f o r nf, n g , and nh c a s e s , the q u a d r u p o l e p o l a r i z a t i o n t e r m A ( Z ) K ( Z ) p ( n , X )q(n, JL- ) c a n be n e g l e c t e d when only two m e m b e r s of the s e r i e s a r e a v a i l a b l e . The i o n i z a t i o n p o t e n t i a l w i l l then be due to d i p o l e p o l a r i z a t i o n A ( Z ) p ( n , Ji o n l y . c . ng s e r i e s . B y a p p l y i n g E q . (8) to 5g, 6g, and 7g, we obtain three s i m u l t a -neous equat ions : I . P . - 328651.9 = 0. 5574A(l+0 . 00534K) I . P . - 328725. 0 = 0. 3584A(l+0 . 00695K) I . P . - 328765.9 = 0. 2393A(l+0 . 0078K) B y s o l v i n g these three e q u a t i o n s , we have I . P . = 328842. 6 A ( Z ) = 388. 8 K ( Z ) = - 1 2 . 0 22. The T e r m C l a s s i f i c a t i o n of Sn V. a. E n e r g y L e v e l s O b s e r v e d . Table X. Odd E n e r g y L e v e l s of Sn V. Con f i g u r a t i o n Desig. J L e v e l Interval 4 d 9 5 p 3 P 2 259554.8 1 268418.9 0 274045.5' 3 F 4 269178.4 3 262739.5 2 273788.6 3 D 3 274824.5 2 269445.8 1 281592.3 1P 1 277012.4 *F 3 280240.2 1D 2 283070.8 9 3 4d 6p P 2 400648.5 1 406097.2 0 414309.6 *P 1 414651.8 -8864. 1 -5626.6 6438.9 11049. 1 5378.7 12146.5 -5448.7 -8212.4 23. Table XI. E v e n E n e r g y L e v e l s of Sn V. Co n f i g u r a t i o n Desig. 10 4d 4 d 9 5 s 9, 4d 6s 4d 5s 9 4d 5d 1 D 'D D D 0 3 2 1 2 3 2 1 2 4 3 2 2 1 0 0 2 4 1 5 4 L e v e l 0.0 183027.7 185481.8 191655.6 193516.7 379399. 1 380618.2 388009.9 388962.7 385129.0 392676.7 395077.7 401714.4 406665.1 411255.5 414318.6 373176.7 379098.4 Interval •2454. 1 •6173.8 •1219. 1 •6173.8 -7547.7 -2401.0 -4950.7 -6997.8 T a b e l XI. cont. C o n f i g u r a t i o n Desig. 9 4d 5d D J 3 2 1 0 3 2 1 4 3 L e v e l 386096.2 379931.3 379955.3 383217.6 380477.3 382023.5 388815. 1 382404.1 Interval -24. 0 •3262.3 D G 4 9 2 -1 Ionization potential (4d 1/3) is 583000 c m (5). In this s p e c t r u m there were sixteen odd and twenty-six even l e v e l s e s t a b l i s h e d . One hundred and seven li n e s have been c l a s -s i f i e d as Sn V t r a n s i t i o n s . 9 9 b. 4d 5s and 4d 6s Configurations. 9 9 The configurations 4d 5s and 4d 6s are examples of configura tions of one s e l e c t r o n and another electron-hole with a r b i t r a r y Jl /4 JL +1 •? s a r e obtained by r e v e r s i n g the sign J v U " 1 the E q . (6). The four energy l e v e l s of the configuration JL ^  ^ +*! a r e given by the following expression: 3 3 3 | = F Q + I./4 i j j J ( G ^ - l / 4 j ^ 2 + 1/4 j?( i + 1) L J L L JL^_ 1 = F - G ^ + 1/2 ( JUl)£*£. B y introducing a coupling p a rameter l | / = i + , where ^~ 4 " 4 • and e x p r e s s i n g the energies i n units of G - ^. + 1) ^ with 1 / 2 ( ^ L ^ + 3 L £ ) a s t n e z e r o l e v e l , we t r a n s f o r m previous r e l a t i o n s into r E ( 3 L ) = -1 E ( 3 L ) = -1 + 2 ^ Table XII. C a l c u l a t e d and O b s e r v e d L e v e l s of 4 d 9 5 s and 4 d 9 6 s of Sn V. Con f i g u r a t i o n D e s i g . J C a l . L e v e l Obs. L e v e l . C a l . -Obs. 9 3 4d 5s D 3 183037.7 183027.7 10.0 2 185081.0 185481.8 -400.8 1 191665.4 191655.6 9.8 1 D 2 193917.0 193516.7 400.3 4 d 9 6 s 3 D 3 379399.0 379399.1 -0.1 2 380565.6 380618.2 -52.6 26. Table XII. cont. C o n f i g u r a t i o n De s i g . 9, 4d 6s J C a l . L e v e l Obs. L e v e l Cal.-Obs. 1 388009.5 388009.9 -0.4 2 389014.4 388962.7 51.7 F i g . 5. The configuration d 9 s in intermediate coupling. C O N C L U S I O N . In this t h e s i s , only 21.7% of the lin e s i n my l i s t s have been c l a s s i f i e d , however, it is b e l i e v e d that since these are the strongest li n e s i n the spectrum, about 60% of the line intensity is contributed by c l a s s i f i e d l i n e s . The b a s i c s t r u c t u r e of the s p e c t r a of Sn III, IV, V have been es t a b l i s h e d i n the c o u r s e of a compre-hensive r e - e x a m i n a t i o n of the spark s p e c t r a of t i n . In Sn III the establishment of forty-eight even and t h i r t y - s i x odd t e r m s have p e r m i t t e d the c l a s s i f i c a t i o n of two hundred and seventy s i x l i n e s . In Sn IV, one hundred and nineteen li n e s have been c l a s s i f i e d as combinations between t h i r t y - f o u r odd l e v e l s and t h i r t e e n even l e v e l s . In Sn V, the establishment of twenty-six even and sixteen odd l e v e l s have p e r m i t t e d the c l a s s i f i c a t i o n of one hundred and seven l i n e s . In p r e v i o u s work, a total of only one hundred and twenty five, f o r t y f i v e , and fifty eight l i n e s were f o r m e r l y c l a s s i f i e d in these spe c t r a , f o r a total of two hundred and twenty eight l i n e s . The present total of c l a s s i f i e d l i n e s is five hundred and two in these three spark s p e c t r a . B I B L I O G R A P H Y . E. U. Condon and G. H. Shortley, "The T h e o r y of A t o m i c  Spectra", (Cambridge U.P. 1.935). B. E d l e n in J . Flugge Handbuch der P h y s i k , V o l . XXVII. (1964). K.B.S. E r i e k s s o n , P h y s i c a l Review, V o l . 102, No. 1, 102-104, A p r i l 1, (1956). K.A.. Dick, MSc. thesis (1963). G. E . Moore, A t o m i c E n e r g y L e v e l s , Vol,III. , C i r c u l a r of the National B u r e a u of Standards 467 (U.S. Government P r i n t i n g O f f i c e , Washington, 1958). R. Tousey, A p p l i e d O p t i c s 1, 679 ( 1962). R.C. Gibbs, abd.H.E. White, P r o c . Nat. A c a d . S c i . 14, 345, 559 (1928). Y.N. J o s h i , Ph.D. thesis (1964). R.E. Honig, Vapor P r e s s u r e Data for The s o l i d and L i q u i d E l e m e n t s . (R.C.A. Review, V o l . XXIII, No. 4, December 1962). R. L . K e l l y . Vacuum U l t r a v i o l e t E m i s s i o n L i n e s . T A B L E X I I I . THE T I N E L I N E L I S T FROM 3 5 0 A TO 9 0 0 0 A W N = W A V E -W L = W A V E -NUMBER I N VACUUM L E N G T H IN VACUUM I F W A V E L E N G T H I S L E S S THAN 2 0 0 0 A W L = W A V E -I 1 = L I N E I 2 = L I N E L E N G T H I N A I R I N T E N S I T Y OF I N T E N S I T Y OF I F W A V E L E N G T H I S B I G G E R THAN 2 0 0 0 A E X P O S U R E 1 E X P O S U R E 2 | i I 3 = L I N E I N T E N S I T Y OF E X P O S U R E 3 I 4 = L I N E I N T E N S I T Y ON S P A R K I N H E L I U M P L A T E S E X = E X C I T A T I O N E S T I M A T I O N A C C O R D I N G TO P O L E E F F E C T S ON S P A R K IN H E L I U M P L A T E S S = S H E N S T O N E S U N P U B L I S H E D D A T A ( 1 9 5 8 ) ( 1 0 ) WN WL I 1 12 13 14 EX C L A S S I F I C A T I O N i 2 8 1 5.9 1 . 8 2 7 8 5 0 9 . 9 2 7 7 0 1 2 . 1 3 5 5 . 1 2 4 3 5 9 . 0 5 4 3 6 0 . 9 9 5 6 1 0 6 9 0 5 8 7 3 1 6 7 0 8 2 6 3 V 4 D Q 5 P 3 D 1 - 4 D 1 0 I S O V 4 D 9 5 P 1 P 1 - 4 D 1 0 I S O ; 2 7 5 5 0 8 . 1 2 7 5 3 1 1 . 8 2 7 3 9 7 8 . 6 3 6 2 . 9 6 6 3 6 3 . 2 2 5 3 6 4 . 9 9 2 7 1 8 6 9 6 7 4 8 7 5 2 i 2 6 9 0 0 0 . 8 2 6 8 4 1 9 . 6 2 6 7 4 8 9 . 0 3 7 1 . 7 4 6 3 7 2 . 5 5 1 3 7 3 . 8 4 7 6 9 2 7 4 6 6 8 3 7 2 0 7 6 6 3 9 3 7 3 7 5 0 0 V 4 D 9 5 P 3 P 1 - 4 D 1 0 1S.0 2 6 5 4 5 5 . 5 2 6 5 2 3 0 . 6 2 5 9 8 7 0 . 1 3 7 6 . 7 1 1 3 7 7 . 0 3 0 3 8 4 . 8 0 8 7 3 0 7 7 6 6 9 6 8 0 7 8 5 1 4 8 2 l 2 5 7 0 4 2 . 4 2 5 6 3 9 8 . 0 2 5 5 1 3 4 . 9 3 8 9 . 0 4 1 3 9 0 . 0 1 9 3 9 1 . 9 5 0 5 1 9 8 8 5 8 9 9 5 2 9 1 2 5 4 9 0 3 . 8 2 5 2 3 1 7 . 2 2 5 0 9 2 3 . 7 3 9 2 . 3 0 5 3 8 6 . 3 2 7 3 9 8 . 5 2 8 6 7 6 7 7 3 9 0 7 9 0 9 i 2 4 9 6 5 0 . 1 2 4 9 5 1 8 . 0 2 4 8 7 4 8 . 5 4 0 0 . 5 6 1 4 0 0 . 7 7 3 4 0 2 . 0 1 2 7 8 3 5 1 8 9 0 9 8 2 3 i 2 4 8 3 6 5 . 6 2 4 8 0 8 2 . 3 2 4 7 6 6 0 . 6 4 0 2 . 6 3 2 4 0 3 . 0 9 2 4 0 3 . 7 7 8 6 9 7 9 0 3 7 1 2 3 6 8 9 0 4 j ! 2 4 7 4 0 2 . 4 2 4 6 1 4 4 . 1 2 4 5 4 1 9 . 9 4 0 4 . 2 0 0 4 0 6 . 2 6 6 4 0 7 . 4 6 5 7 5 5 9 0 3 8 6 9 7 3 7 4 8 5 ,t i i 2 4 4 4 4 6 . 2 4 0 9 . 0 8 8 6 3 8 6 7 4 3 5 0 2 4 4 1 8 6 . 5 4 0 9 . 5 2 3 5 6 6 5 17 2 8 1 2 4 0 8 6 9 . 8 4 1 5 . 1 6 2 7 0 6 7 0 3 3 5 0 2 3 9 9 3 1 . 3 4 1 6 . 7 8 6 9 4 1 2 3 8 9 1 0 . 9 4 1 8 . 5 6 6 7 0 0 8 5 3 2 3 8 7 5 6 . 9 4 1 8 . 8 3 6 6 7 9 8 2 9 2 3 8 6 0 9 . 3 4 1 9 . 0 9 5 7 5 1 8 8 7 2 3 6 7 1 4 . 7 4 2 2 . 4 4 9 7 3 7 7 4 4 4 2 2 2 3 5 7 7 6 . 8 . 4 2 4 . 1 3 0 8 2 7 7 6 5 6 7 7 2 3 4 4 7 2 . 7 4 2 6 . 4 8 9 8 1 0 9 2 1 2 3 2 7 4 1 . 8 4 2 9 . 6 6 1 3 8 4 7 3 6 3 7 4 2 3 2 5 3 4 . 3 4 3 0 . 0 4 4 3 0 7 7 2 2 2 6 8 2 3 2 4 6 2 . 5 4 3 0 . 1 7 7 7 0 9 2 7 2 2 3 1 4 2 6 . 8 4 3 2 . 1 0 2 6 3 9 6 5 3 2 8 2 2 3 0 7 8 4 . 4 4 3 3 . 3 0 5 8 4 5 9 0 7 2 3 0 4 1 5 . 3 4 3 3 . 9 9 9 7 7 8 8 0 0 2 3 0 2 8 3 . 4 4 3 4 . 2 4 7 8 4 3 2 2 9 8 6 4 . 7 4 3 5 . 0 3 9 6 9 5 6 4 6 2 2 9 2 7 0 . 6 4 3 6 . 1 6 6 8 0 2 9 1 4 2 2 9 1 0 9 . 9 4 3 6 . 4 7 2 8 1 6 8 4 3 I V 5 S 2 S 1 / 2 - 4 D 9 5 S ( 3 D ) 5 P 4 P 3 / 2 2 2 8 6 6 9 . 4 4 3 7 . 3 1 2 5 9 8 8 10 6 8 3 2 2 8 4 8 5 . 1 4 3 7 . 6 6 5 . 6 1 9 8 1 1 6 4 8 2 2 7 5 6 0 . 7 4 3 9 . 4 4 3 7 9 8 7 7 9 7 8 9 2 2 6 9 8 6 . 9 4 4 0 . 5 5 4 6 0 9 7 3 3 2 2 6 2 1 2 . 0 4 4 2 . 0 6 3 4 2 6 4 8 8 2 5 8 2 2 5 5 3 7 . 6 4 4 3 . 3 8 5 9 2 8 2 2 5 3 8 9 . 0 4 4 3 . 6 7 7 8 2 7 9 3 2 2 2 4 9 1 1 . 1 4 4 4 . 6 2 0 9 3 5 2 2 4 4 0 2 . 2 4 4 5 . 6 0 4 4 6 3 7 5 6 3 9 4 2 2 2 9 9 6 . 8 4 4 8 . 4 3 7 9 3 3 ' V 4 D 9 6 P 1 P 1 - 4 D 9 5 S 3 D 1 2 2 2 6 5 5 . 2 4 4 9 . 1 2 5 8 5 2 7 9 8 8 3 1 V 4 D 9 6 P 3 P 0 - 4 D 9 5 S 3D1 2 2 2 4 8 7 . 3 4 4 9 . 4 6 4 8 2 3 7 6 7 7 8 2 2 2 1 8 7 0 . 8 4 5 0 . 7 1 3 8 4 4 9 2 7 2 2 1 3 1 4 . 4 4 5 1 . 8 4 6 7 7 8 7 9 9 2 2 1 1 3 5 . 0 4 5 2 . 2 1 2 7 0 8 6 4 0 V 4 D 9 6 P 1 P 1 - 4 D 9 5 S 1D2 2 2 0 7 8 9 . 0 4 5 2 . 9 2 1 ' 9 4 6 ' 8 8 9 2 2 0 6 1 3 . 1 4 5 3 . 2 8 2 7 3 2 8 2 9 7 9 6 V 4 D 9 6 P 3 P 1 - 4 D 9 5 S 3D2 2 1 9 1 2 7 . 0 4 5 6 . 3 5 6 7 8 2 7 5 6 7 3 8 2 1 8 8 3 2 . 2 4 5 6 . 9 7 1 7 8 5 9 1 1 • 2 1 8 1 5 4 . 3 4 5 8 . 3 9 1 8 4 3 9 4 1 -2 1 7 9 6 9 . 4 4 5 8 . 7 8 0 9 3 7 2 1 7 6 2 2 . 9 4 5 9 . 5 1 1 2 2 4 8 14 2 4 2 V 4 D 9 6 P 3 P 2 - 4 D 9 5 S 3 D 3 2 1 7 1 3 5 . 5 4 6 0 . 5 4 2 8 13 8 7 9 C.1 Ul 1- r-o ro r-r- o CO CO 00 CM rH CO CO CO •4- CM oo 00 CO NO r-LT\ CM oo CM -H -4 NO \D <t 4" <)" CO C\J LA r- -4 o LO i—i i—i CM CM (XI Q on to tn ON Q 4" I CM Q_ oo a v O o Q vO ON r- r-co CO i—I Lf\ CO oo in r--r- r- NO r-* o r-vO O CO r- m r--4- m m NO v O NO <t- 4- <f IT. ON LO 4" CM CO vO CM i—I rH CO in 4- 4" •—I i—l rH CM CM CM a co LO o Q 4-I rH Q. 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