{"Affiliation":[{"label":"Affiliation","value":"Science, Faculty of","attrs":{"lang":"en","ns":"http:\/\/vivoweb.org\/ontology\/core#departmentOrSchool","classmap":"vivo:EducationalProcess","property":"vivo:departmentOrSchool"},"iri":"http:\/\/vivoweb.org\/ontology\/core#departmentOrSchool","explain":"VIVO-ISF Ontology V1.6 Property; The department or school name within institution; Not intended to be an institution name."},{"label":"Affiliation","value":"Physics and Astronomy, Department of","attrs":{"lang":"en","ns":"http:\/\/vivoweb.org\/ontology\/core#departmentOrSchool","classmap":"vivo:EducationalProcess","property":"vivo:departmentOrSchool"},"iri":"http:\/\/vivoweb.org\/ontology\/core#departmentOrSchool","explain":"VIVO-ISF Ontology V1.6 Property; The department or school name within institution; Not intended to be an institution name."}],"AggregatedSourceRepository":[{"label":"AggregatedSourceRepository","value":"DSpace","attrs":{"lang":"en","ns":"http:\/\/www.europeana.eu\/schemas\/edm\/dataProvider","classmap":"ore:Aggregation","property":"edm:dataProvider"},"iri":"http:\/\/www.europeana.eu\/schemas\/edm\/dataProvider","explain":"A Europeana Data Model Property; The name or identifier of the organization who contributes data indirectly to an aggregation service (e.g. Europeana)"}],"Campus":[{"label":"Campus","value":"UBCV","attrs":{"lang":"en","ns":"https:\/\/open.library.ubc.ca\/terms#degreeCampus","classmap":"oc:ThesisDescription","property":"oc:degreeCampus"},"iri":"https:\/\/open.library.ubc.ca\/terms#degreeCampus","explain":"UBC Open Collections Metadata Components; Local Field; Identifies the name of the campus from which the graduate completed their degree."}],"Creator":[{"label":"Creator","value":"Bhatia, Kuldip Singh","attrs":{"lang":"en","ns":"http:\/\/purl.org\/dc\/terms\/creator","classmap":"dpla:SourceResource","property":"dcterms:creator"},"iri":"http:\/\/purl.org\/dc\/terms\/creator","explain":"A Dublin Core Terms Property; An entity primarily responsible for making the resource.; Examples of a Contributor include a person, an organization, or a service."}],"DateAvailable":[{"label":"DateAvailable","value":"2011-06-16T23:06:03Z","attrs":{"lang":"en","ns":"http:\/\/purl.org\/dc\/terms\/issued","classmap":"edm:WebResource","property":"dcterms:issued"},"iri":"http:\/\/purl.org\/dc\/terms\/issued","explain":"A Dublin Core Terms Property; Date of formal issuance (e.g., publication) of the resource."}],"DateIssued":[{"label":"DateIssued","value":"1969","attrs":{"lang":"en","ns":"http:\/\/purl.org\/dc\/terms\/issued","classmap":"oc:SourceResource","property":"dcterms:issued"},"iri":"http:\/\/purl.org\/dc\/terms\/issued","explain":"A Dublin Core Terms Property; Date of formal issuance (e.g., publication) of the resource."}],"Degree":[{"label":"Degree","value":"Doctor of Philosophy - PhD","attrs":{"lang":"en","ns":"http:\/\/vivoweb.org\/ontology\/core#relatedDegree","classmap":"vivo:ThesisDegree","property":"vivo:relatedDegree"},"iri":"http:\/\/vivoweb.org\/ontology\/core#relatedDegree","explain":"VIVO-ISF Ontology V1.6 Property; The thesis degree; Extended Property specified by UBC, as per https:\/\/wiki.duraspace.org\/display\/VIVO\/Ontology+Editor%27s+Guide"}],"DegreeGrantor":[{"label":"DegreeGrantor","value":"University of British Columbia","attrs":{"lang":"en","ns":"https:\/\/open.library.ubc.ca\/terms#degreeGrantor","classmap":"oc:ThesisDescription","property":"oc:degreeGrantor"},"iri":"https:\/\/open.library.ubc.ca\/terms#degreeGrantor","explain":"UBC Open Collections Metadata Components; Local Field; Indicates the institution where thesis was granted."}],"Description":[{"label":"Description","value":"Emission spectra of Indium have been photographed over the spectral range from 340A\u00b0 (177A\u00b0 in 2nd order) to 9500A\u00b0 using the disruptive electrodeless and spark in helium sources. About 4000 lines of Indium have been measured and 36% of these lines are classified as belonging to the spectra of InI,InII, Inlll, InlV and InV.\r\nThe analyses of Inlll and InlV have been revised and extended to include 4d\u00b9\u00bans(n=5 to 12), `4d\u00b9\u00bans(n=5 to 9), 4d\u00b9\u00band (n=5 to 9) and 4d\u00b9\u00banf(n=4 to 7). Polarisation theory has been applied to 4d\u00b9\u00bang(n=5 to 9) and 4d\u00b9\u00banh (n=6 to 9) series and the ionization potential deduced from this is reported to be 226191.3\r\ncm\u207b\u00b9. The dipole polarizability of the 4d\u00b9\u00ba core is estimated to be 3.48a\u2080\u00b3 . Most of the expected terms of 4d\u2079 5s5p and 4d\u2079 5s6s are established for the first time. Some of the levels of 4d\u2079 5s5d are also added as well as some levels from the higher configurations 4d\u2079 5s7s and 4d\u2079 5s6d. In triply ionised Indium the new additions are to the 4d\u20795d, 4d\u2079 6d, 4d\u20785s and 4d\u20796p configurations. Houston's theory of intermediate coupling has been successfully applied to 4d\u2079ns (n=5,6 and 7) terms. Tentative values are given to several levels of 4d\u20785s5p and 4d\u20794f terms. The double limit of InlV is calculated from 4d\u2079ns series as 461875 cm\u207b\u00b9 and 468989 cm\u207b\u00b9. Experimental results are compared with the theoretical\r\ncalculations for some of the configurations of Inlll and InlV.","attrs":{"lang":"en","ns":"http:\/\/purl.org\/dc\/terms\/description","classmap":"dpla:SourceResource","property":"dcterms:description"},"iri":"http:\/\/purl.org\/dc\/terms\/description","explain":"A Dublin Core Terms Property; An account of the resource.; Description may include but is not limited to: an abstract, a table of contents, a graphical representation, or a free-text account of the resource."}],"DigitalResourceOriginalRecord":[{"label":"DigitalResourceOriginalRecord","value":"https:\/\/circle.library.ubc.ca\/rest\/handle\/2429\/35526?expand=metadata","attrs":{"lang":"en","ns":"http:\/\/www.europeana.eu\/schemas\/edm\/aggregatedCHO","classmap":"ore:Aggregation","property":"edm:aggregatedCHO"},"iri":"http:\/\/www.europeana.eu\/schemas\/edm\/aggregatedCHO","explain":"A Europeana Data Model Property; The identifier of the source object, e.g. the Mona Lisa itself. This could be a full linked open date URI or an internal identifier"}],"FullText":[{"label":"FullText","value":"ANALYSIS OF DOUBLY AND TRIPLY IONISED INDIUM by KULDIP S. BHATIA B.Sc.(Hons. ), Panjab University, (Chandigarhj,India. M.Sc.(Hons.), Panjab University, (Chandigarh),India. A THESIS SUBMITTED IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE DEGREE OF DOCTOR OF PHILOSOPHY in the Department of PHYSICS We accept t h i s thesis as conforming to the required standard THE UNIVERSITY OF A p r i l , BRITISH 1969. COLUMBIA 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 of the r e q u i r e m e n t s f o r an advanced degree a t the U n i v e r s i t y of B r i t i s h C olumbia, I a g r e e t h a t the 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 . a n d Study. 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 of t h i s t h e s i s f o r s c h o l a r l y p u rposes may be g r a n t e d by the Head o f my Department or 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 not 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 . Department The U n i v e r s i t y o f B r i t i s h Columbia Vancouver 8, Canada 'Theories are the millstones and the experimental data the grains fed into them. It i s obvious 'that the millstones alone cannot produce any thing useful however long they may turn,(Theory i s working on i t s e l f ) , But the q u a l i t y of f l o u r i s determined by the q u a l i t y of the grain and the rotten grain cannot y i e l d n u t r i t i o u s f l o u r . Therefore experimental physics i s the necessary prerequiste fo r the healthy development of our Science' Lord Kelvin. i i Table of Contents Abstract v Acknowledgements v i -Chapter I Introduction 1 Chapter II Experimental Techniques 4 Chapter III General Theory . 9 Rydberg Series and Moseley Diagrams 10 Regular and Irregular Doublet Laws; 14 - Lande's Interval Rule. 15 Selection Rules. 17 Chapter IV Indium I I I . .20 4d 1 0ns Series. 20 4d 1 0np Series 21 4d*^nd Series. . . . . . . ' . 2 3 4 d 1 0 n f Series. 24 P o l a r i s a t i o n formulae for Hydrogenic Series. 26 Terms A r i s i n g From Configuration 4d 5snl. 29 Theo r e t i c a l Calculations for 4d 5s5p. 36 Chapter V Indium IV 44 9 4d 5p Configuration. 45 \u00ab I l l 4d ns Configuration. 47 o 4d 5s Configuration 49 9 -4d 6s Configuration. 50 4d^7s Configuration and Series Limit. 53 4d 5s Configuration. 55 9 4d 5d Configuration. 58 -4d96p, 4d 94f-and 4d 85s5p Configuration. 62 4d 6d Configuration. 63 Conclusions and Suggestions for further work. 7 1 Bibliography. 72 Appendix .74 iv L i s t of Tables 1. n* for 4d ns Series in Isoelectronic Sequence of I n l l l . 20 2. n* for 4d*\u00b0nd Series i n Isoelectronic Sequence of I n l l l . 24 3. P o l a r i s a t i o n formulae applied to ng and nh se r i e s of I n l l l . 28 4. Extrapolations to predict the lowest l e v e l of 4d 95s5p in I n l l l . 30 5. Extrapolation of the multiplet i n t e r v a l s of 4 P and 4D i n 4d 95s5p. 31 6. Comparison of calculated and observed l e v e l s of 4d 95s( 3D)5p of I n l l l . 38 7. Energy Levels of Indium III. 39 8. Comparison of calculated and observed l e v e l s of 4d 95p i n InlV. 46 9. Comparison of calculated and observed l e v e l s of 4d 9ns series i n InlV. 52 10. J notation for d d configuration in InlV. 60 11. Energy Levels of InlV. 64 L i s t of Figures 1. Graph of $ - n - n* vs. absolute term values of 4d 1 0ns se r i e s . 22 2. Graph of & - n - n* vs. absolute term values 10 of 4d nd s e r i e s . 25 9 3. Levels of config.4d 5s5p of Agl iso-sequence. 33 4. Term rel a t i o n s h i p s in successive Indium Ions. 35 9 5. Intermediate coupling for 4d ns in Pdl i s o e l e c t r o n i c sequence. 51 8 2 6. 4d 5s structure i n i s o e l e c t r o n i c sequence of Pdl. 59 V ABSTRACT Emission spectra of Indium have been photographed over r j \u2022the s p e c t r a l range from 340A\u00b0 (177A\u00b0 i n 2nd order) to 9500A0 using the dis r u p t i v e electrodeless and spark i n helium sources. -About 4000 l i n e s of Indium have been measured and 36% of these l i n e s are c l a s s i f i e d as belonging to the spectra of InI,InII, I n l l l j I n l V and InV. The analyses of I n l l l and InlV have been revised and extended to include 4d l 0ns(n=5 to 12), 4d 1 0np(n=5 to 9J, 4d 1 0nd (n=5 to 9) and 4d^nf(n=--4 to 7). P o l a r i s a t i o n theory has been applied to 4d*<\")ng(n=-5 to 9) and 4d\"^nh (n=*6 to 9) series and the i o n i z a t i o n p o t e n t i a l deduced from t h i s i s reported to be 226191.3 cm\"\\ The dipole p o l a r i z a b i l i t y of the 4d*\u00b0 core i s estimated to be 3 9 9 ' 3.48a c . Most of the expected terms of 4d 5s5p and 4d 5s6s are 9 established for the f i r s t time. Some of the l e v e l s of 4d 5s5d are also added as well as some l e v e l s from the higher configurations 9 9 4d 5s7s and 4d 5s6d. In t r i p l y ionised iridium the new additions are to the 9 9 8 2 9 4d 5d, 4d 6d, 4d 5s and 4d 6p configurations. Houston's theory 9 of intermediate coupling has been su c c e s s f u l l y applied to 4d ns (n=5,6 and 7) terms. Tentative values are given to several l e v e l s 8 Q of 4d 5s5p and 4d 4f terms. The double l i m i t of InlV i s calculated 9 -1 -1 from 4d ns series as 461875 cm and 468989 cm Experimental r e s u l t s are compared with the t h e o r e t i c a l c a l c u l a t i o n s for some of the configurations of I n l l l and InlV. ACKNOWLEDGEMENTS I am much indebted to my supervisor Prof.A.M.Crooker for h i s kind assistance and encouragement a l l through t h i s work. He has given generously of his time and expert advice on numerous d i f f i c u l t questions. I wish to express my thanks to Dr. Rolf Mehlhorn of Lawrence Radiation Laboratory at Berkeley for doing^the t h e o r e t i c a l c a l c u l a t i o n s for some part of t h i s work. I am thankful to the members of my supervisory committee, Dr,B.Ahlborn, Dr.A.J.Barnard, and Dr.F.W.Dalby for h e l p f u l comments and suggestions.I have a great pleasure to thank Prof.A.G.Shenstone of Palmer Physics Laboratory, Princeton University, for c r i t i c a l examination of t h i s thesis and h e l p f u l comments. Technical assistance of M\/s. J.Lees and A.J.Fraser i s much appreciated. Mr.V.S.Surana's help i n the preparation of t h i s text i s thankfully acknowledged. I am thankful to The National Research Council and the Department of Physics for the f i n a n c i a l assistance during t h i s work. F i n a l l y I wish to record my appreciation of the help and encouragement rendered to me by my wife P r a t i p a l K. Bhatia.She s a c r i f i e d much in keeping me r e l i e v e d from the worries of household problems. CHAPTER I 1 . ' i INTRODUCTION ' At the 50th anniversary meeting of Optical Society of America i n 1966, Prof .Bengt Edle'n gave an excellent review of 'Frontiers i n Spectroscopy'^ 1', In that he remarks about the big 1 boom of t h i s f i e l d during the decade centered arounfl 1930. Spectroscopy was one of the most cherished f i e l d of physics. But as Edlen puts i t , \"The high tid e i n e v i t a b l y c a r r i e d some rubbish with i t \" and as a r e s u l t the big volume of data created a chaos. Most of the spectra were barely touched upon and some of the adequately done turned out to be completely wrong. A look into the tables prepared by Shenstone^)^ Meggers^ 3' and D i e k e ^ ) and summarised i n a recent (5) report reveals the fragmentary knowledge we have about the most of these spectra. We know that the number of d i f f e r e n t spectra that can be produced by 102 elements i n a l l stages of i o n i s a t i o n t o t a l s 5253.Most of these spectra may each consist of several thousand l i n e s and the more complex spectra .of rare earth l i k e elements several tens of thousands of l i n e s , leaving us with a v i r t u a l l y inexhaustible f i e l d . In recent years there has been an active renewed i n t e r e s t i n the study of atomic spectra p a r t i c u l a r l y because of the much needed data f o r some of the new areas of research i n hot plasmas, s o l a r spectra, s o l i d state and to interpret the large quantum of data p i l i n g up r a p i d l y by the new techniques of spectroscopy applied to extra t e r r e s t r i a l astrophysics. The ever increasing demands of our old customers i n Astronomy i s another j u s t i f i c a t i o n of the objective of t h i s research. Most of the previous work i n spectroscopy was confined to the e a s i l y accessible region of v i s i b l e and near u l t r a v i o l e t spectrum. Infra red was opened up a f t e r the big boom was over .and s t i l l remains to a large extent an unexplored f i e l d . The other end of the spectrum below 2000A0 c a l l e d Vacuum U l t r a v i o l e t or XUV had to wait the necessary developments of techniques and instrumentation i n p a r t i c u l a r high r e f l e c t i o n gratings, Vacuum systems and s e n s i t i v e detectors, along v\/ith the means to produce these spectra. XUV i s by f a r the largest part of the o p t i c a l spectrum and i s also the most important as f a r as the atomic structure i s concerned. The need to work i n t h i s region was well recognised as e a r l y as i n 1928 when the pioneer i n t h i s f i e l d Prof. Lyrsmn^J v\/rote\/'In the l a s t fourteen years the extreme u l t r a v i o l e t has changed from a l i t t l e known region to a well \u2022 recognised and important part of the spectrum\". In t h i s report vie have recorded the spectra over a wide range of, 340A\u00b0 to S5500A\u00b0 but a major part of the work involves the vacuum u l t r a v i o l e t . (7) Looking through The Atomic Energy Level T a b l e s v ' compiled by Mrs. Moore S i t t e r l y i t i s found that i n the Pdl and Agl sequence the spectra of P d l , A g l , A g l l , C d l l and C d l l l are very well done by Shenstone and are highly r e l i a b l e . The other member of t h i s sequence SnIV and SnV has also been analysed by Shenstone and Y\/hite and has been re c e n t l y revised and extended i n t h i s Lab by ( 8) C.M.V\/u , thus Indium looks to be the missing l i n k of t h i s important group of complex spectra. ^ Some- ten years back Indium was studied i n t h i s laboratory by Nodwell ' and he could e s t a b l i s h some of the basic l e v e l s of q 2 these spectra. In p a r t i c u l a r h i s f i n d i n g of 4d 5s i n I n l l l ' was very^jgratifying. But unfortunately he had very l i m i t e d f a c i l i t i e s to work i n the region where most of doubly and t r i p l y ionised indium spectra, l i e . Since then a new three meter vacuum grating spectrograph has been b u i l t i n t h i s laboratory which can very well record the whole region from 340A0 to 2400A0 i n one exposure on 30\" p l a t e s . Also since h i s two meter grazing incidence spectrograph was not a stigmatic one, he could not e x p l o i t much the spark i n Helium source which-gives very important and ind*.sponsible information about the various i o n i s a t i o n stages. Measuring accuracy at present - i s d e f i n i t e l y -ten -times more than i t was at that time mainly because of the use of Grant Automatic Comparator and the better dispersion i n the vacuum region. The use of computers for the reduction of data and a n a l y s i s , eliminates'some of the human error. The a v a i l a b i l i t y of more accurate and new standards of reference f o r the c a l c u l a t i o n of-,wavelengths i s an important factor f o r the better accuracy of our data. Also since then there has been a s i g n i f i c a n t development i n the sources to produce the spark spectra of i o n i s e d indium. Keeping a l l these things i n mind we had taken up t h i s project. The various corrections and extensions we have made to the previous analysis are given i n t h i s thesis. In b r i e f ' the i n t r o d u c t i o n can be best concluded by st a t i n g the three main ob j e c t i v e s of t h i s project as : ( i ) To obtain the l i s t of Indium l i n e s i n the region 340A\u00b0(177A\u00b0 i n the 2nd order) to 9500A0 and t h e i r r e l a t i v e i n t e n s i t i e s i n d i f f e r e n t spark sources. ( i i ) To confirm and correct the energy l e v e l s of I n l l l and InlV est a b l i s h e d by previous workers and f i n a l l y ( i i i ) To extend the term scheme, for the higher configurations. 4 CHAPTER I I EXPERIMENTAL TECHNIQUES The spectrographs used for t h i s work are the three meter vacuum spectrograph b u i l t and designed here i n t h i s laboratory and which i s mounted in l i n e with a Hilger Spectrograph E(478), Littrow -mounted with interchangable qurtz and glass prism. The vacuum spectrograph i s designed to photograph a wide range from 340A\u00b0 (177A\u00b0 i n 2nd order) to 2440A0 on the 30\"x2\" Q-2 emulsion plates from l'lford. Angle of incidence was 9\u00b0-40' and the grating was manufactured by Bauch and Lomb ruled with 1200 l i n e s \/mm, g i v i n g a r e c i p r o c a l \"dispersion of 2.775 A\u00b0\/mm. It was blazed for 1300A0.' Pressure maintained i n the vacuum chamber was always less than lullg except i n some exposures with spark i n He source where the source pressure was more than 10 cm of Hg, and-it'was d i f f i c u l t to maintain the pressure d i f f e r e n t i a l . However in such cases\" the pressure never was more than 2u i n the vacuum tank of the spectro-graph. V\/e simultaneously recorded the prism spectrum by putting the E(478) spectrograph on the other side of our double window sources. This was done because we strongly f e e l that the source conditions could never be exactly the same when i t i s run separately for recording d i f f e r e n t regions of the spectrum. This i s p a r t i c u l a r l y important when we consider the r e l a t i v e i n t e n s i t i e s of l i n e s over the whole range. The prism spectrograph records X2300A0 to X9500A0 on three 10\" plates. Thus e s s e n t i a l l y we had recorded a region from 340A\u00b0 to 9500A0 i n one shot without changing the source conditions. Two exposures v\/ere always taken on each plate of vacuum spectrograph, one of the exposures being r e l a t i v e l y much shorter 5 than the other f o r a comparison. Photographic plates used are: ^ X340A0 to 3000A0 I l f o r d Q-2 plates. \/ X3000A0 to 6500A0 I l f o r d HP-3 plates. X4500A0 to 9500A\u00b0 Kodak 1-K plates. (Developed i n D-19 developer) Q-2 and HP-3 plat e s were developed with the Johnson AZOL mixed with one part i n twenty parts of water. Light Sources The.two main l i g h t sources used for t h i s work v\/ere the d i s r u p t i v e e l e c t r o d e l e s s discharge as described by Minnhagen^-1-0) and the spark i n He source as described i n Shenstone's^1'1\"^ ^ a ^ r . on S i l l with a l i t t l e modification to make these su i t a b l e for Indium. (12) .From vapour pressure data \" the vapour pressure of indium can be c a l c u l a t e d * approximately from the expression l o g 1 ( ) P = A + BT\" 1 from tables * 1 2 * we note that for P=10\"4 rnmHg, T=1000\u00b0K and -3 P. = 10 mmHg T=1100\u00b0K thus substitute these values i n the above equation and t h i s w i l l give us the values for A = 7.0 and B= -11000\u00b0K So indium has rather a low vapour pressure and a veryweak or no discharge was possible below 800\u00b0C and we had to use a heating oven which could s a f e l y go to a temperature of 1500\u00b0C though a s a t i s f a c t o r y discharge v\/as possible at about. 1200\u00b0C corresponding to which the vapour pressure i n the discharge tube v\/as about .10 . \"mmllg. There i s a l i m i t to the maximum temperature because the softening point for the qurtz tube we use i s also near 1400\u00b0C. Even for 1200\u00b0C the S i l i c o n spectrum i s f a i r l y well excited. A great advantage of working at' these high temperatures i s that the plates turn out to be very clean and p r a c t i c a l l y free from impurity bands and f o r that reason v\/e may suggest that before any run a tube should always be heated to the maximum temperature.so as to bake out the impurities and then one Eay work at the desired temperature. The operating frequency of the discharge v\/as '3 At. Hertz fed through a bank of solar condensors with capacitance of ,005iifarads. The rapid oxidation of the c o i l was avoided by using an a l l o y NichromeV (Ni + Cr + Al) which could stand much longer and many more experimental runs. The spark i n He had no problem other than the f a c t that because of the low melting point of In i t would not stay f o r more than a few minutes i n the upper electrode which i s quite important for g e t t i n g the best pole e f f e c t . One can use a water cooled electrode or otherwise we d r i l l e d some f i n e holes i n the car ban cup and molten indium was forced out of these holes to st r e t c h i n t o wires forming beads at the surface which could remain suspended f o r a longer period of time. With t h i s exposure we had taken several exposures at d i f f e r e n t pressures of He and we observed that working at a higher pressure could give higher excitations but under t h i s . c o n d i t i o n i t was d i f f i c u l t to maintain the pressure d i f f e r e n t i a l from the vacuum chamber. Also higher pressure being pumped out at a f a s t e r speed gave better e x c i t a t i o n data, ye are sure to have excited I n l l l and InlV pretty well. We could compare our e x c i t a t i o n data with the one we had from Crooker's plates \"taken i n Shenstone's .laboratory i n Princeton. More d e t a i l s of the experimental set up are (13) ! -described i n the thesis of K.A.Dick and that of K.Lyall^- 1-' 1'. The plates were measured on the Grant Automatic Line measuring Comparator which had a plate carriage of 250 mm. This sophisticated machine could measure sharp l i n e s within the accuracy of + 1 micron, and i t v\/ould d i r e c t l y read the transmission of the l i n e s on the scale of 0 to 1000. For each plate t h i s transmission was normalised to read the most cle a r part of the plate as 990 and the complete cut o f f of the l i g h t to read 5. A r e l a t i o n of the transmission reading on the card to the r e l a t i v e i n t e n s i t y of the (15) l i n e i s worked out f o r t h i s comparator by Crooker and Wu . We had modified t h i s comparator to punch also one of 12 comments about the l i n e to specify the character of the l i n e . Calculations of wavelength and wave numbers are done by the computer I.B.M. 7044 using a polynomial f i t for the vacuum region and Hartmann dispersion formula for the prism plates. In the region below Xl7o0A\u00b0 we used C,N and 0 standards as given i n Edlen's l i s t ^ ^ ) and since there are not many standards avai l a b l e to be used above 1930A\u00b0 for the polynomial f i t , v\/e had used s i l i c o n standards- taken from Toresson^ 1?) and R a d z i e m s k y e t a * papers. Even otherwise both the l i n e s ?t1930Ao and X2297A\u00b0 the only avail a b l e sta-ndards are str o n l y blended by the Indium l i n e s . The appearance of s i l i c o n standards was an unexpected advantage of working at that high temperatures. 8 For the prism plates we used i r o n standards taken from Crosswhite and only for X greater than 6500A\u00b0 we had to use the neon l i n e s as the standards. However the prism l i n e s were not wore accurate than \u00a3 .05A\u00b0. 9 CHAPTER III GENERAL THEORY The theory discussed i n t h i s chapter i s much les s comprehensive than the t i t l e suggests. Only those aspects of the theory of atomic spectra are b r i e f l y discussed which are d i r e c t l y r e l a t e d to the analysis of I n l l l and InlV. Modern theory of complex spectra stated with the fundamental paper of S l a t e r w h o gave with h i s diagonal sum method a very powerful t o o l f o r c a l c u l a t i n g the energy l e v e l s of a system of tv\/o or more electrons. However i n the following considerations we v \/ i l l not follow the approach of c a l c u l a t i o n of each energy l e v e l but on the other hand we w i l l summarise some of the t h e o r e t i c a l guidelines for- the p r e d i c t i o n of a p a r t i c u l a r configuration and how to make the semi-empirical estimates about the f i n e structure of that c o n f i g u r a t i o n . I l l u s t r a t i o n of the applications of these w i l l be given f o r p a r t i c u l a r cases i n the chapters on I n l l l and InlV. For d e t a i l e d c a l c u l a t i o n s of energy l e v e l s from the quantum mechanical treatments the reader i s r e f e r r e d to the standard text,'Theory of Atomic Spectra (TAS)' by Condon and S h o r t l e y ^ 2 1 ^ or the o r i g i n a l papers i n l i t e r a t u r e . In some cases these c a l c u l a t i o n s might be vex'y h e l p f u l at l e a s t to give a very s a t i s f a c t o r y check on the a n a l y s i s but as we know that i n any complex spectrum so many other unknown perturbations are present that to expect a very close agree-went between the theory and the experiment may not be possible. Series i n any spectrum are supposed to behave i n a well predicted r e g u l a r i t y but i t happens not too i n f r e q u e n t l l y that a l l attempts to make to f i t a formula to them may f a i l , not due to the error i n 10 a n a l y s i s , but because of these unknown perturbations. The -calculation of these perturbation has shown i n some cases that the s h i f t s of l e v e l s by hundreds and even thousands i s not very improbable;. Thus i t should not be a cause to disturb i f one finds the l e v e l s very f a r from where one had expected them. Most h e l p f u l l guide to predict the region where one should search for the l e v e l s of a configuration i s the extrapolation from the neighbouring analysed spectra of an i s o e l e c t r o n i c sequence. In case of I n l l l and InlV we were fortunate to have the support of Shenstone's e x c e l l e n t analysis of the preceding members of these i s o e l e c t r o n i c sequences. The basis of a l l spectroscopic rul e s i s the R i t z combi-nation p r i n c i p l e which states that the wave numbers of any spectrum l i n e can be expressed as the difference between two terms of a system of terms c h a r a c t e r i s t i c of the atom or i n other words the d i f f e r e n c e between two terms gives r i s e to a s p e c t r a l l i n e whose frequencey y i s given by Bohr's r e l a t i o n \u2022 J> s E 2 \" E l . (3.1) h and i n terms of wave numbers y = 2 _ L _ = T X - T 2. .....(3.2) he v\/here h i s the Plank's constant and c i s the v e l o c i t y of l i g h t i n vacuum. T^ and Tg are the absolute term values or terms which for the one e l e c t r o n system with nuclear charge Z can be written as 1 1 T n RZ 2\/n* 2 ...... (3.3) R- the Rydberg Constant i s R = - m i s the mass of the electron \u00b0h and e the charge. Equation (3.3) shows that the spectra of a l l hydrogenic l i k e spectra are s i m i l a r except f o r the increse of wavenurnber p scale by a factor of Z . In practice i t i s found that the term values are larger i n comparison to the hydrogenic terms which can be mathematically expressed by wri t i n g the above r e l a t i o n as 2 RZ (n- S ) 2 \u00a3> i s c a l l e d the quantum defect which takes d i f f e r e n t values fo r each seri e s but i s almost independent of n. Usually the denominator i n (3.4) i s replaced by n* and represents n - e f f e c t i v e , that i s e f f e c t i v e p r i n c i p a l quantum number. When there are N electrons out side the nucleus, the charge Z on the nucleus w i l l be neutralised by these loosely bound electrons c o n s t i t u t i n g the atomic core so that the net charge experienced by an electron reduces to Z-(N-l) = 1| and Eq.(3.4) can now be written as (n-5)^ n* Rydberg Series and Moseley Diagrams: Most of the early work i n spectroscopy was i n the d i r e c t i o n of f i n d i n g r e l a t i o n s to represent the term s e r i e s . If E i s the r e l a t i v e terra value counted upward from the ground state and E^ the l i m i t when the atom i s ionised, The absolute term value i s defined as R Tabs. = E\u00a3 \" E - g\"~ n* A s e r i e s of terms with the same L and J but with n(the p r i n c i p a l quantum number) increasing by u n i t step i s c a l l e d a Rydberg Series. Depending upon L-0,1,2,3,4,..... the se r i e s are named as Sharp s e r i e s , P r i n c i p a l s e r i e s , D i f f u s e s e r i e s , Fundamental s e r i e s and so on. The names are purely h i s t o r i c a l though they do represent to some extent the character of the l i n e s a r i s i n g from these s e r i e s . As we go along the s e r i e s the quantum defect S approaches a constant value asymptotically: hence by loc a t i n g the observed differences between the two consecutive members of the s e r i e s , En -- En,j_\u00a3 oil the ava i l a b l e t a b l e s v J J' of the differences 2 2 R (1\/n* - l\/(n*-i-l)'' ) , one may calcu l a t e n* and also obtain E\u201e and E n i l . Once tv\/o members of the serie s are calcula t e d i n n n-t- x absolute term values, one may predict the unknown members of the ser i e s by the reverse process. An estimate of the increase i n n* for the next member can be best made from the corresponding series i n i s o e l e c t r o n i c sequence. For large n and also for higher l,the procedure i s quite accurate and i f such a s e r i e s i s av a i l a b l e the io n i s a t i o n p o t e n t i a l of the ion or the atom can be p r e c i s e l y known. (23) In Fowler's ,'Report on Series i n Line Spectra' \"\u00b0 various formulae have been stated to give a s a t i s f a c t o r y f i t to the s e r i e s . To f i r s t approximation the Ritz formula may be written 16 as \u2022 \u2022 . 6 - + BT' <3 '^ J \" T 1 or i f we define the reduced term value t = \u2014-vy- ==.... ~. R \u00a7 * n* 2 and the curve $ = a + Bt be plotted i t should give a s t r a i g h t l i n e . Any experimental deviation of the curve from the s t r a i g h t l i n e can be further corrected by including the higher order terms i n t or w r i t i n g g \u00ab a + Bt + 7 - t 2 + j i t 3 + More often the s e r i e s are perturbed by the foreign terms and i n case we know the energy E D of the perturbing term we can account for the perturbation by adding to the n* a term a\/(E n-E G) with the appropriate sign to make the i n t e r a c t i o n repulsive. Of course the appreciable i n t e r a c t i o n occurs only i f the terms have the sarae p a r i t y and J value. The absolute term value of the energy l e v e l may equally w e l l be expressed as ; T n = _Bl|iUL m_s&\u00b1*)* - ( 3 - 6 ) n n where s and P are screening and penetration parameters r e s p e c t i v e l y and as stated before i s the net charge on the electron i n a system of N electrons. For I n l l l and InlV the ^ i s 3 and 4 . It represents the degree of i o n i s a t i o n of the ion being considered. From t h i s we arive at a very simple but usefu l conclusion that i f s i m i l a r terms of the ions of an i s o e l e c t r o n i c sequence are plo t t e d as T n\/R vs. Z i t should y i e l d a st r a i g h t l i n e with slope 1\/n and the intercept on the -axis as the measure of the screening parameter. This i s a very h e l p f u l and f a i r l y r e l i a b l e way to 14 predict the approximate position of a term i f the same i s known in the other members of i t s i s o e l e c t r o n i c sequence. Regular and Irregular Doublet Laws: ' Above formula (3.6) c l e a r l y shows that the wave numbers corresponding to any t r a n s i t i o n between the two terms of same n i s l i n e a r l y dependent on Z or for the same n i n a spectrum 5 = ?n - T n = R \/ n 2 < 2 z)'(*i \" % ) + ( V \" - f ) = AZ + B -This also follows from Sommerfelds formula for one electron spectra i.e. T(n,j) = R\/n2 ( Z - S ) 2 + ~4 ( Z - s ) 4 { ^ J J 2 - 3\/4) ...(3.7) a here i s the f i n e structure constant and for nj. = = n and assuming j , = jo = j also s, = s we have the r e l a t i o n for the *\u2022 -t r a n s i t i o n which c l e a r l y i s determined by the d i f f e r e n t screening of the two o r b i t s and hence they are c a l l e d the screening doublets. The l a t t e r name i s i n anology with the doublets f i r s t observed i n X-rays. Regular Doublet Law^ On the vector model we can calculate the fin e structure of a multiplet by wr i t i n g the spin o r b i t i n t e r a c t i o n energy as r = i > ( i . s ) where n 3 1(1+1\/2)(1+1) ^ = R. \u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014\u2014-\u2014\u2014 '....(3.8) and since i . s --4a\u00b1l\u00bb--llltll.:.Sl2tl>-_ .....(3.9) and f o r a single electron the doublet term has j = 1 \u00b1 1\/2 we have the energy difference of the doublet term as 15 Ra 2Z 4 E\u201e = (3.10) n 3 n For a non-hydrogenic o r b i t we of course have to take into account the screening e f f e c t due to the core of electrons and we must replace Z i n the above expression by (Z-s). Thus a plot of ( E\/Rch) against Z for the same doublet i n the i s o -e l e c t r o n i c sequence should be a straight l i n e and from th i s one can also estimate the screening constant or the e f f e c t i v e charge. The a p p l i c a t i o n of the regular doublet law can be well 2 9 2 i l l u s t r a t e d by c a l c u l a t i o n of D separation of 4d 5s i n I n l l l , Z Ion E S 47 Agl 4471.9 23.69 48 C d l l 5363.7 23.31 49 I n l l l 6900 23.0 the observed value i s 6848.0 Cm . Lande's Interval Rule: In t h i s study of ionised Indium we are not dealing with a case of pure Russell-Saunders coupling. But since the deviations from L.S coupling change smoothly as we go along the i s o e l e c t r o n i c sequence therefore we can have a f a i r i n d i c a t i o n of the multiplet s p l i t t i n g by extrapolating the observed Lande's factor for each multiplet. In L.S coupling the r e l a t i o n (3.9) can be extended to many electron configurations by replacing j , l and s of a single 16 electron by the t o t a l L, S, and J of the term. The i n t e r v a l . between the two l e v e l s of J and J - l w i l l be L J ~ L J - 1 = J which means that the i n t e r v a l s are thus proportional to the r\u00ablar\"ger of the two J values. This i s known as the Lande's Interval Rule. For two electrons Goudsmit and Humphreys^ 2 4^ have derived the formula which gives us the s p l i t t i n g f actor PCn^ljL, n 2 l 2 i SL) f o r various terms and configurations i n terms of the parameters of the i n d i v i d u a l electrons. According to this': T L(L+1) + l w l i ' i - l ) - l o ( V l ) S(S+1) + s i ( s 1 + l ) - s 2 < S 2 + f* = p -. --- X \u2014 2L(L + 1 ) 2S(S +1) L(L+1) + 1 2(1 2+D ~ l i d i + D S(S+l)+s 2(s2+l)'-s 1(s 1+l) v 2L(L + 1) 2S(S +1) (3.11) \/ ^>ft\u00a3 9 P = - ---- can be obtained from 4d 5s i n InlV. 2 For a configuration of more than tv\/o electrons p i s calculated by considering the parent term quantum numbers as l i and s and added to that i s the electron 1 JL Cd and s 2 giving us the f i n a l term with t o t a l L and S. As f o r the 9 3 4 \u2022configuration 4d 5s( D)5p, the term D can be c a l c u l a t e d by s u b s t i t u t i n g li=2, s - j ^ l , 12=1, s2\"=+l\/2 and L=2,S~l-~. For some of the most common terms t h i s i n t e r v a l f a c t o r i s c a l c u l a t e d 1 7 i n TAS and a p p l i c a t i o n of t h i s formula applied to I n l l l and Iniy i s also i l l u s t r a t e d i n the following chapters. An add i t i o n a l advantage of c a l c u l a t i o n of f7 i s that i t gives us a rough estimate of the t o t a l spread of a multiplet, because with the change i n coupling though the mutual i n t e r v a l s between the members of the multiplet change yet their t o t a l spread approximately remains the same. Selection Rules: Much before the concept of parity was introduced the people i n spectroscopy were well aware that the t r a n s i t i o n s are only possible between one set of level s and another group ..of l e v e l s , t r a n s i t i o n s are not observed among the le v e l s of the same group. This l a t e r came out to be the natural consequence of quantum mechanics that i n an e l e c t r i c dipole r a d i a t i o n the odd p a r i t y l e v e l s can combine only with the even p a r i t y config-urations and vice versa, unless there i s an external e l e c t r i c f i e l d . The p a r i t y of a configuration i s determined from the sum of o r b i t a l angular momentum quantum numbers i . e ^ l . and the i p a r i t y i s odd or even depending upon th i s sum. The t r a n s i t i o n s due to quadrupole radiations are i n p r i n c i p l e possible but the pr o b a b i l i t y of.such t r a n s i t i o n s i s so small that the l i n e s should be rather weak. We have observed one such t r a n s i t i o n between 4d ]^5p 2 P ^ a n d 4d 1 06p 2P,y^\u00b0f * n H I . Otherwise the par i t y rule i s obeyed rather s t r i c t l y . As we go away from the Russell-Saunders Coupling the designations of l e v e l s i n the L.S scheme loses i t s meaning and the le v e l s are characterised by the t o t a l angular momentum 16 J . Normally the t r a n s i t i o n s .are only possible when J changes by 0 or + 1 except that J=0 to J=0 i s rigorously forbidden. For some of the t r a n s i t i o n s we have observed a change of J by \u00b1 2.but again such s p e c t r a l l i n e s are extremely weak and the high nuclear moment of In i s large l y responsible for these t r a n s i t i o n s . In the other two fundamental s e l e c t i o n rules of -L.S coupling that f o r any t r a n s i t i o n L=0 or \u00b11 and S=0, the v i o l a t i o n s are so frequent that these rules do not seem to e x i s t at a l l . T r a n s i t i o n s in which S\/ 0 are c a l l e d intercombination l i n e s and some of these are very strong l i n e s i n our spectra. Equally strong are the l i n e s for t r a n s i t i o n s where L changes by \u00b12 but f o r 2 we did f i n d the i n t e n s i t y appreciably -decreased though some exceptions are not ruled out. For a long time i t was assumed that in a t r a n s i t i o n only one electron w i l l jump at a time so that the strongest l i n e s w i l l a r i s e fi'om the t r a n s i t i o n s between the terms b u i l t up on the same state of ion. This i s only an approximate rule p a r t i c u l a r l y when the spectrum i s so complex that the wave-functions of various configurations can pa r t l y overlap and the t r a n s i t i o n s with double electron jump due to configuration mixing, are quite possible. In C d l l l and i n InlV we could e s t a b l i s h most of the l e v e l s of 4d 5s by looking at i t s combinations with the 4d^5p terms, and the l i n e s are not that weak as one would expect f o r these double electron jumps. If the selection; rules are v i o l a t e d the i n t e n s i t y rul e s are v i o l a t e d as much. The only guide l i n e we used regarding 19 the i n t e n s i t i e s was the comparison with the corresponding t r a n s i t i o n s i n Ag and Cd spectra. Most of the strong l i n e s i n these spectra were found to be equally strong i n Indium. However we did not depend much on the in t e n s i t y consideration for the analysis p a r t i c u l a r l y when the i n t e n s i t i e s are very s e n s i t i v e to the unknown conditions of discharge i n the l i g h t sources. 20 CHAPTER IV INDIUM III To s t a r t the analysis v\/e f i r s t made the squai~e arrays for the known l e v e l s of I n l l l and t r i e d the Bockstan f i t(25) using the t r a n s i t i o n values from our own l i n e l i s t . This necessitated changing the values of the established l e v e l s by a few wave-numbers and some of the l e v e l s had to be completely rejected. 4d*^ns -Series: 10 2 Ground state of I n l l l i s 4d 5s a n d previous workers had found 4d''^6s, 7s and \u2022 8s which are found to be correct except that each i s lower by about 4 Cm \\ We have added the next four members of t h i s s e r i e s . The n* calculated f o r each l e v e l i s pretty close to the predicted value. A regu-l a r i t y of n* along the i s o e l e c t r o n i c sequence i s shown i n Table No.l. ' Table No.1 (n* f or the 4d^ns serie s i n the i s o e l e c t r o n i c sequence of Inlll') Term Agl C d l l I n l l l g for I n l l l 4d 5s 1.341 1.794 2.090 2.910 6s 2.432 2.867 3.154 2. 846 7s 3.450 3.885 4.171 2. 829 8s 4.456 4.893 5.180 2. 820 9s 5.459 5.897 6.184 2.816 10 s 6.461 6. 899 7.187 2.813 l i s 7.462 7.901 8.189 2.811 12s 8.463 8.902 9.191 2.809 A plot of the quantum defect for t h i s series against the term value T a b s o l u t e i s shown in f i g . ( 1 ) and i t i s very nearly a s t r a i g h t l i n e as expected from the Eq.(3.5A). We however did not use t h i s s e r i e s to calculate the i o n i s a t i o n p o t e n t i a l of I n l l l as the p o l a r i s a t i o n theory applied to the 4d*\u00b0ng serie s which c l o s e l y obeys the Rit z formula w i l l give a much more accurate value for the Limit. 4'd'^hp Series: Only the f i r s t two members of t h i s s e r i e s were known 1 0 before and the 4d 8p reported by Nodwell does not seem to be r i g h t . The d i f f i c u l t y i n f i n d i n g t h i s series i s understandable from the f a c t that t h i s i s strongly perturbed due to the inte r c o n f i g u r a t i o n perturbations from the 4d^5s5p terms. Fine structure i n t e r v a l for the JV can be calculated from the r e l a t i o n for absolute term value i.e T a b s - R V n * - 2 ( d n * ) T a b s dT \u2014 \u2014 su b s t i t u t i n g f o r T a j 3 S n* we have dT, the doublet separation 2 2 p _ C P3\/2 ~ V 2 ~ ~ n*3\" the constant C t h e o r e t i c a l l y i s supposed to be constant a l l along the s e r i e s , but a c t u a l l y i t decreases for the higher ^ - -members. As an example we can determine C using the f i r s t two members of t h i s series which were known before. C.G. of the doublet 4d 1 05p i s calculated to be 2. 865 2.855 U 2.845 L 2.835 L 2;825 L 2.815 L 2. 805 20 30 40 50 60 70 80 30 \u2022 Term Value Fig.l-. Graph o f $ =n-n* vs. absolute term values f o r 4 d l 0 n s s e r i e s i n I n l l l ICO 23 10 2 2< 2Pl\/2) + 4 ( 2 P 3 \/ 2 ) C.G of 4d i U5p ^P = \u2014 2 + 4 ' = 60079 and the corresponding n*-2.439 This gives us the value of the constant C as = 63009.0 Cm\"'\" S i m i l a r l y c a l c u l a t i o n of C f o r 4d^\u00b06p gives the value 57175.0 showing that the constant decreases by about 9 o\/o By extrapolating the increase i n n* f o r the next member of the s e r i e s from the i s o e l e c t r o n i c sequence we can approximately 2 10 locate the term P of 4d 7p at about 177500 corresponding to n* = 4.5000 and for the doublet separation we extrapolate from the f i r s t two known members so that, 4 d 1 0 5 p dn* = .0317 6p dn* = .0289 7p dn* .0270 approx. therefore the predicted doublet separation for 2p amounts to be around 580 Cm\"\"* and the actual difference found to be -1 = 605 Cm . The corresponding constant C i s 54675.0 cm The next member 4d*^8p s i m i l a r l y i s predicted to have the doublet separatio of 300 Cm * and the observed difference i s -1 ' \u2022 286 Cm . In spi t e of these close predictions we have not 10 been able to extend t h i s s e r i e s beyond 4d 9p, mainly due to the presence of 4d^5s5p configuration . 4d^^nd Series: tv>\u00ab O n l y A f i r s t three members of t h i s s e r i e s were known before. We have added the next 3 members. This s e r i e s , l i k e the sharp s e r i e s , also follows a quite regular n* and does 2 not seem to be perturbed, n* for the '\u2022s' c o n , P a r e c J with the corresponding valu s for Agl and C d l i . 24 Table No. 2 (n* for the 4d*^nd s e r i e s i n the i s o e l e c t r o n i c sequence o f l n l l l ) y \u2022! i Term Agl C d l l I n l l l f or I n l l l 4 d 1 05d 2.979 3.066 3.179 1.821 6d 3.987 4.093 4.213 1.787 7d 4.990 5.104 5.228 1.772 8d 5.992 6.109 6.234 1.766 9d , - 7.112 7.238 1.762 lOd - 8.114 8.239 . 1.761 Though one can reasonably well predict the next few members but i t defied a l l our e f f o r t s for the search of these l e v e l s . The other s t r i k i n g feature of t h i s series i s the f i n e structure s p l i t t i n g for the doublets. This difference decreases as we go along the series according to the regular 2 doublet law. The same r e l a t i o n s we used for the P separation should be applicable here also. Again the quantum defect plotted against the term value f a l l s f a i r l y well on a str a i g h t l i n e as shown i n the f i g . 4 d 1 0 n f Series: We could not extend the fundamental seri e s as far as we had hoped and the e s s e n t i a l reason i s again the mutual perturbation of t h i s series from the terms a r i s i n g due to 9 4d 5s5p configuration as i t was for the P r i n c i p a l Series. Only the f i r s t member of t h i s s e r i e s i s retained from the terms 26 reported before. Nodwell had mentioned 4d*\u00b05f to be a very -1 - i close doublet at 184892 Cm separated only by 3Cm . We do _1 2 accept the l e v e l 184892 Cm to be a r e a l l e v e l as F 7 \/ 2 , but the other l e v e l ^F$\/2 l i e s about 129 Cm * higher than ^ 7 \/ 2 So i n going from 4d'\"\u00b04f to 5f the normal doublet term becomes 2 inverted F and same i s the case for C d l l . The best check to these l e v e l s was from t h e i r combinations with the 4d*^ng series and we can see that the i n t e n s i t y for these t r a n s i t i o n s decreases i n a very systematic way as we go to the higher member t r a n s i t i o n s . Since the p o l a r i s a t i o n theory could not be applied to t h i s s e r i e s , we conclude that the f - o r b i t s are penetrating and perturbed i n the doubly ionised Indium. P o l a r i s a t i o n Formulae for the Hydrogenic Series: C a l c u l a t i o n of P o l a r i s a t i o n parameters shows that except i n the case of Agl the f - o r b i t s are hardly non-penetrating i n t h i s sequence. Even for the case of Agl ,the parameter A(Z) defined below i s constant only for the f i r s t two members i.e 4 d 1 0 4 f and 4d 5f, while i t i s about ten times less in 4d x06f. We believe that the 6f term may be perturbed due to i n t e r -configuration i n t e r a c t i o n s or probably needs a further confirmation, For Cdl'I and I n l l l the fundamental series corresponds to a system of penetrating o r b i t s thus as stated above , the p o l a r i s a t i o n theory i s not applicable. But the application to the 4d*^ng and 4d*\u00b0nh serie s i s found to be s a t i s f a c t o r y and i s treated i n the following discussion. The two parameter formula derived from the theory developed by Born,Heisenberg and W a l l e r ^ 2 ^ has been used. 27 According to t h i s the term defect aZ G R 3n 2 - i ( I + 1 ) P h 2 a c 3 n5(^-l\/2)(e).(^+l\/2)(\/ + l)(^+3\/2) = A(Z)P(n,g) where A(Z) i s substituted for and can be calculated 2 a D 3 i f the f i r s t two terms of the series are known. This formula can be further modified to include the quadrupole p o l a r i s a b i l i t y and i s given in Eq.(20.6) of Edlen's a r t i c l e ^ 2 ? ) . A p = T - T h = A(Z)P(n,\u00a3) ^ 1 + K(Z)q(n,\u00a3) j
ng and 4d*^nh series are shown i n Table No.3. Table No.3 (The p o l a r i s a t i o n formula applied to ng and nh series of Term Calculated Observed Term Calculated 4d 1 05g 186526.5 1S6526.5 4d 1 06h 19S724.0 6g 198654.0 198654.0 7h 20S012.0 7g 205966.5 205966;5 8h 210741.3 Sg 210710.8 210712.5 9h 213987.0 9g 213965.0 213966.8 10g 216289.8 - \u2022 The term value for 4d 1^6h i s established with as l i t t l e Observed 206011.C 210742.C 213986.5 one t r a n s i t i o n , but the t h e o r e t i c a l c a l c u l a t i o n i s enough support to the r e a l i t y of t h i s l e v e l . 29 Terms A r i s i n g From The Configuration 4d 5snl: Levels with odd P a r i t y : \u2022 An attempt has been made to f i n d the l e v e l s belonging to the configuration 4d 95s5p involving the excited 9 core 4d 5s. Nodwell has reported some of the l e v e l s of t h i s configuration but these do not show s a t i s f a c t o r y combinations according to our\" l i n e l i s t and the e x c i t a t i o n data. He himself had indicated the need for further confirmation of these l e v e l s . We have rejected a l l h i s l e v e l s but one for which the desig-nation i s changed.lie had predicted the whole configuration -1 about 7000 Cm below the region where i t should a c t u a l l y l i e . To predict t h i s configuration we consider the energy required to r a i s e a 5s electron to the 5p o r b i t . This 9 9 happens i n various cases notably i n going from 4d 5s to 4d 5p i n InlV, 4d1<\"*5s to 4d'\"<\">5p in I n l l l and we can extrapolate 9 9 9 for going from 4d 5s to 4d 5s5p i n t h i s case by looking at the s i m i l a r differences i n the i s o e l e c t r o n i c sequence. These differences are tabulated i n Table No.4 and by a l l these con-9 siderations we predict that the lowest l e v e l of 4d 5s5p should be f a i r l y close to 164000 \u00b1 1500 Cm\"1. We e s t a b l i s h the lowest l e v e l 4 P 5 \/ 2 a t 162759.0 Cm\"1 and a l l the l e v e l s with J = 1\/2 and 1 1\/2 above t h i s go strongly to the ground state. We have observed almost a l l of these t r a n s i t i o n s i n both the electrode-less and spark i n Helium sources and their e x c i t a t i o n deduced from pole e f f e c t , confirm that these belong to the spectrum 3 0 o f doubly ionised Indium. \u2022 Table No.4 (Extrapolation to predict the lowest l e v e l of 4d 95s5p i n I n l l l ) T r a n s ition 4d 95s 2-4d 95s5p 4d 5s-4d 5p 9 9 4d 5s - 4d 5p Ag 25981 (Agl) 29552 (Agl) Cd 36931 ( C d l l ) .443.36 (Cdll) 41009 53359 (A g l I ) ( C d l l I ) In 49000 + 1500 57184 ( I n l l l ) 65214 (InlV) Addition of a 5p electron to the parent 4d 95s( D) gives r i s e to ihe terms 4P, 4D, 4F, 2P, 2D and 2 F while the addition of 5p electron to the parent 4d 95s( 1D) w i l l give the other set of 2 ? 2 doublets i.e P, \"D and F. ~ Mul t i p l e t s p l i t t i n g can be calculated by using Eq.(3.11) by s u b s t i t u t i n g *1~2> s i ~ * > a n d l 2 r = 1 ' s 2 ~ + 1 \/ \/ 2 f o r where \/ * - - 1 W2 4 P (J>1 and S=3\/2) P = (V - 1\/6 %y 4D (L=2 and S--3\/2) r = i \/ i 8 ^ , + 10\/18 r' 4 F (L=3 and S=3\/2) P - 4\/9 p'+ 1\/9 %-p For 2pop of th i s parent we have to use S 2 ~ -1\/2 and 2P(L=l,S-l\/2) = 3\/1 + 1\/2 \\ 31 \"D(L=2,S=l\/2) p = 10\/6 p \u20221\/6 %p F(L-3,S-1\/2) \/\"I = 4\/3 p ' - 1\/3 ^ S i m i l a r l y we can ca l c u l a t e these i n t e r v a l factors for the 2 9 1 other set of PDF due to the parent 4d 5s( D) by replacing s^=l by ST =\"0 and the calculated r e s u l t s are 2 P = -1\/2 %q 2 D = + 1\/6 % ^ 2 F ' = + 1\/3 %ff> A comparison of the extrapolated i n t e r v a l s and the corresponding observed i n t e r v a l s for ~p and 4D multiplets are given i n Table No. 5. 4 F i s not considered because of the missing l e v e l ^9\/2* *r^ie o b s e r v e < 3 i n t e r v a l s are reasonably close to the extrapolated values. (Extrapolation Table No. 5. of the multiplet i n t e r v a l s 4 of P and 4 9 D in 4d 5 Terms Agl C d l l I n l l l \" Observed 4 p 5 \/ 2 ~ 4 p3\/2 4 4 P3\/2- P i \/ 2 2.15xp 1.85x\/*' -1053 2.20xT7 i . s o x r -1477 2.25x\/~' 1.75X\/-1 -1900 2.27X\/7 1.72XA7 -2013 4 4 \u00b07\/2~ D5\/2 4 4 D5\/2\" D3\/2 4 4 D3\/2 \" D i \/ 2 l.lOxp 3.60X\/H 2.8oxP 0.35xp 2.98xp 4.17x P O.OSxf7 2.3 x T 4.7 x p 0.09x\/^ 2.28xP 5.13x\/^ S -374 -426 -470 -517 32 . The term system i s plotted graphically i n f i g . ( 3 ^ and i t i s found that the graphs go reasonably well i n the expected way. On the y-axis i s plotted(E - E 0)\/^*J-C where E Q i s the reference l e v e l from which the energy i s counted upward and i n the plot of t h i s configuration the reference l e v e l E Q i s 2 9 2 taken to be D3\/2 of 4d 5s . \u2022 o 9 i .T h e o r e t i c a l l y PDF of 4d 5s(^D) parent should l i e as much above the other 2PDF of 4ct 95s(3 D) parent as i s the ^ 1 9 difference between \"D and D of 4d 5s in InlV, but these terms are found to be i n a much higher region though we are \u2022\u2022not surprised because the same i r r e g u l a r i t y i s observed i n the case of Agl and C d l l . Levels with Even p a r i t y : 9 The configuration 4d 5s6s i s easy to predict a f t e r 9 o we have established 4d 5s\"5. The\" n* for t h i s i s 2.03 and the next series member should have n* around 3.09 which predicts t h i s configuration to be near 245000 Cm 1 . Nodwell had i d e n t i f i e d these l e v e l s much below t h i s region at about 205000 Cm *, but since he looked for these l e v e l s by the combinations with 9 ^ his 4d 5s5p te. ms which i s not accepted by our analysis, we rule out these l e v e l s as unreal. To e s t a b l i s h these l e v e l s i s d i f f i c u l t , p a r t l y due to the fact t h i s configuration l i e s about 20000 Cm-* above the i o n i s a t i o n l i m i t of I n l l l and partly due to the t r a n s i t i o n s from some of these l e v e l s being d i f f u s e and not appearing too strong on our spectrograms taken with moderate disx-ersion. The autoionisation w i l l make the analysis more d i f f i c u l t , i n that the l i n e s are broadened enough to c = 1.21 34 increase the wnvenumber tolerance and necessitate an i n d i v i d u a l study Of the l i n e s . The other main reason i s the lack of support from the corresponding analysis of C d l l . None ^ of these terms i s reported i n the l a t t e r analysis by Shenstone. Some of the terms e a r l i e r reported by Takahashi are completely rejected by S h e n s t o n e ^ mainly because he too reported these l e v e l s much below the i o n i s a t i o n l i m i t . The r e v i s i o n of this C d l l spectrum i s currently being done in th i s laboratory to decide the correct analysis. However once we have the correct region for these l e v e l s the fin e structure of the configuration can then be traced from the parent configuration of InlV and InV. The structure can be represented diagramatically as shown in Fig.4. Also one can extrapolate the multiplet s p l i t t i n g of 4D from the Lande 's i n t e r v a l factor as we did i i * the case of other m u l t i p l e t s belonging to the odd par i t y l e v e l s of 4d 95s5p. 4 2 We could i d e n t i f y D and D a r i s i n g from the parent 4d 95s( 3D) but the other 2D of 4d 95s( 1D)6s l i e s so much above 9 that i t i s e s s e n t i a l l y mixed with the configuration 4d 5s5d thus i s d i f f i c u l t to name with cer t a i n t y . 9 The configuration 4d 5s5d i s incomplete and the main reason i s our complete ignorance of th i s configuration i n any other member of i t s i s o e l e c t r o n i c sequence. We do hope that i t w i l l be possible to complete t h i s analysis a f t e r the current projects i n Ag and Cd are completed. Since i t i s much easier to choose some of the obvious ' ., I n V . I n l V I n l l l 9 q 9 1 (4d ) (4d 5s) 4d 5s6s Term r e l a t i o n s h i p s in successive Inditun Ions. (SCHEMATIC) 36 l e v e l s of 4d 95s7s and 4d 95s6d because of the high v\/ave numbers of the t r a n s i t i o n s involved, we have added some of the l e v e l s belonging to these configurations. We believe that these two configurations are overlaping so much that i t i s not very meaningful to assign names other than the J values. The r e l a t i v e energy l e v e l s of I n l l l are given i n Table No.7. Theore t i c a l Calculations for 4d 95s5p: Since t h i s i s a three electron configuration which gives more than one term of a p a r t i c u l a r kind so the ordinary diagonal sum method of t h e o r e t i c a l c a l c u l a t i o n s for e l e c t r o s t a t i c energies w i l l y i e l d only the sum of th e i r (29) energies. Racah used his tensor method to overcome t h i s d i f f i c u l t y . His r e s u l t s for the e l e c t r o s t a t i c energies i n 9 the p a r t i c u l a r case of d sp are of i n t e r e s t to us and are given below: 4 p \" V 7 F 2 - G p 2 P r \" F o \" 7 F 2 + G d + 1 0 G l * G p 2 + G d 2 + ^ 0 G l 2 - G p G d - 1 0 G 1 (G p +G d) 4D = F 0 + 7 F 2 - G p ^ = F 0 + 7 F 2 + G d * < G p 2 + G d 2 - G p G d ) 1 \/ 2 4 F _ F -2F -Gp 2 F = F o - 2 F 2 + G d + 1 5 G 3 \u00b1 G p 2 +G d 2 +225G 3 2-G pG d-15G 3(G p +G d) At our request Mehlhorn at Lawrence Radiation Laboratory did the calculations for the level s of thi s configuration using the observed lev e l s we had sent to him. 37 In Table No.6 his calculated l e v e l s are compared with the observed Values. Because of the large mean error the Slater parameters are not well defined, but t h i s i s probably a r e f l e c t i o n of configuration i n t e r a c t i o n rather than the error i n our analysis. In f a c t these c a l c u l a t i o n s should have been made i n context with the Agl i s o e l e c t r o n i c sequence which we hope would give a better f i t to the observed l e v e l s . For example these c a l c u l a t i o n s predict 4F5\/2 - 4F7\/2 to be as close as 2 Cm*** but the extrapolation from the i s o -e l e c t r o n i c sequence shows that t h i s should be around 200 Cm-1-The Calculated Parameters are: GjCdp) G,(ps) 4781.6 1700.4 17973.3 2873.6 F 2(dp) G 2(ds) G 3(dp) 25748.4 2942.8 10615.8 Fo 201614.8 38 Table No.6 (Comparison of calculated and observed lev e l s of 4d^5s5p) Term 4 4 4 P 2 \u00a7 * 1 * \"Pi 2 Calculated 163893.0 166998.2 169538.5 Observed 162753.6 167339.0 170811.6 1134.4 -340.8 1273.1 F4ir lF l 1689B0.3 168988.4 170401.0 167262.2 167727.0 170888.0 1728.3 1134.0 487.0 D 3 | 2 173897.3 173541.2 175728.1 177719.4 174310.2 174357.6 175538. 7 178187.5 -412.9 -816.4 189.4 -468.1 5p' 3| 177732.2 180052.9 176531.0 179928.6 1201.0 124.3 5p' P]! 2 p i 2 178019.0 1804.09.7 178616.0 179321.0 -597.0 1088.7 5p' 180567.9 181921.7 180945.0 182361.5 377.1 439.8 39 Config. 4 d 1 0 ( 1 S ) 5 s Table No. 7 (Energy Levels of I n l l l ) Desig 5s J Level \u2022\u2022\u2022 0.0 Interval 4 d 1 0 ( 1 S ) 5 p 5p 5p# 0 * 57184.0 61527.3 4343.3 4 d 9 ( 2 D ) 5 s 2 5 s 2 2 D 2\u00a7 115572.0 l l 122420.1 -6848.1 4 d 1 0 ( 1 S ) 6 s 6s Oir 126879.9 4d 1\u00b0( 1S)5d 5d 2 D 128457.7 2-it 128747.8 290. 1 4 d 1 0 ( 1 S ) 6 p 6p -p* o | 144588.6 145926.3 1337.7 4d 1\u00b0( 1S)4f 4f 3| 161973.8 161982.1 8.3 4d 95s( 3D)5p 5p' *p* 2\u00a7 0| 162758.6 167339.1 170811.6 -4580.5 -3472.5 4d 95s( 3D)5p 5p' F* 4| 1* 167262.2 167727.3 170888.0 -465.3 -3160.7 4 d 1 0 ( 1 s ) 7 s 7s 0 ! 169434.6 40 Table No. 7 (Cont.) Config. Desig. 4 d 1 0 ( 1 S ) 6 d 6d T) 1| 2* Level 17053 5.8 170719.1 Interval 183.3 4d 95s( 3-D)5p 5p' 4D* 3| i i . 174310.2 174357.6 175538.7 178187.5 \"47.4 -1181.1 \u20222648.8 4d 95s( 3D)5p 5p' JF* 2| - 3| 176531.2 179928.6 3397.4 4 d 1 0 ( 1 S ) 7 p 7p 0| 1| 177264.3 177868.7 604.4 4d 95s( 3D)5p 5p f 2P* 0| 178616.5 179321.0 -704.5 4d 95s( 3D)5p 5p' 2D* 1| 180945.0 182361.5 1416.5 4 d 1 0 ( 1 S ) 5 f 5f \"F* 3\u00a7 2|-184894.6 185024.3 -129.7 4dl\u00b0( 1S)5g 5g %r. AJL 1 G 4-|,3| 186526.5 4d 95s( 1D)5p 5p\" 2F* ;: 3| 189346.8 194901.1 -5554.3 41 Table No. 7 (Cont.) Config. 4d 95s( 1D)5p Desig. 5p\" 2P* J 1-1 Level \u2022\u2022\u2022 188063.9 191508.5 Interval -3444.6 4d 95s( 1D)5p 4d 1\u00b0( 1S)8s 4 d 1 0 ( 1 S ) 7 d 5p' 8s 7d l 1 \u20222. \"D 0\"^ 1| 2| 192848.3 189374.4 190038.2 190135.5 97.3 4 d 1 0 ( 1 S ) 8 p 8p P* 0| 1| 193522.3 193808.5 286.2 4 d 1 0 ( 1 S ) 6 f 6f 2 F * 3| Z 2 198348.7 198199.3 -150.6 4 d 1 0 ( 1 S ) 6 g 6g 2 G 4-|-,3| 198654.0 4 d 1 0 ( 1 S ) 9 s 9s 0| 200363.7 4d 1\u00b0( 1S)8d 8d JD 1| 200780.2 2| 200836.5 56.3 i n 1 2 4 d l u ( S)9p 9p P* 1|,0| 202136.4 4d 1\u00b0( 1S)7f 7f 3-|,2| 205828.0 4d 1\u00b0( 1S)7g 7g 2 G 4|,3-| 20596S.5 42 Table No. 7 (Cont.) Config. Desig. Level \"\" Interval . ,10,]. 4d ( S)7h 10 1 4d ( S)10s 4d- L O( AS)9d 7h 10s 9d 2TT,', H* 5|,<\u00a7 206011.0 D 12 2^ ^2 207068.5 207339.4 207382.6 43.2 10 i 4d ( xS)8g 8g G 41,3-1- 210712.5 4 d 1 0 ( 1 S ) 8 h 8h JH* 5\u00a3,4i 210742.0 10 1 4d ( S j l l s l i s Ok- 211460.3 4 d 1 0 ( 1 S ) 1 0 d lOd D 1-1-,2| 4d 1 C V s)9g 9g G 4-|,3i 213966.8 4 d l 0 ( 1 S ) 9 h 9h 2H* 5^,4| 213986.2 4 d 1 0 ( 3 S ) 1 2 s 9 1 4d 55(^0)6s 12s 6s' 'D 3 1 2-1 0| 214497.3 238830.2 239909.4 244603.0 -1079.2 -4693.6 4d 95s( 3D)6s 6s' 2D l 1 X 2 244661.3 246354.0 -1692.7 43 Table No.7(eont.) Config. Desig. Level Interval 4d 95s5d 5d' 4d 95s( 3D)7s 4d 5s6d 6d 1 ol 247550. 2 2 . ^ 248134. 6 3 249009. 4 4 o i . 251095. 6 5 252560. 1 6 252992. 5 7 i - l 255783. 9 8 2 i 258173. 6 9 \" 2 i ' 260347. 0 10 1| 261025. 6 11 2-1 261364. 2 12 3-1 264237. 7 13 2-1 264763. 9 4D 3 i 2 i 293519. 0 1-1 295849. 1 o-l 297703. 3 14 11 295207. 5 15 ^2 \u00bb A 2 296122. 5 16 299266. 9? 17 i i 299921. 2 18 ? 300118. 5 19 \u00b0 i 300308. 0 20 301410. 2? -2330.1 -1854.2 44 CHAPTER V ,\/ INDIUM IV The previous analysis i s by Gibbs and White(^O) V ; J I O c l a s s i f i e d 36 l i n e s between 472.8A\u00b0 to 1725A\u00b0 . They established a l l the l e v e l s belonging to the configurations 4d*^(ground \" 9 9 s t a t e ) , 4d 5p and 4d 5s. Nodwell revised t h i s spectrum but there i s not any s u b s t a n t i a l change i n the previous analysis except that his values are closer to our values for the t r a n s i t i o n s from odd l e v e l s to the ground state. But again a l l h i s l e v e l s are consistent l y lower by 48 Cm\"\"* as compared to our d a t a . A l l these t r a n s i t i o n s to the ground state l i e i n the f a r u l t r a v i o l e t region where we believe our data to be more r e l i a b l e and also we have observed a l l these t r a n s i t i o n s i n the 1st, 2nd, 3rd and 4th orders . Except for t h i s change we have accepted designations of the terms to be correct. We have also observed a l l the expected t r a n s i t i o n s between these configurations, both i n spark i n He and the electrodeless sources. The e x c i t a t i o n data from the sj>ark i n He has further confirmed the previous analysis. Nodwell's a d d i t i o n a l l e v e l s which he a t t r i b u t e s to the 4d 96s and 4d 96p are rejected for the lack of s u f f i c i e n t support from our l i n e l i s t . Mehlhorn made the t h e o r e t i c a l 9 c a l c u l a t i o n s also, for 4d 5p terms and the mean error of 759 wavenumbers seems to be large but there i s not much doubt as to the correctness of these terms. We have extended t h i s analysis now to include most 45 of the expected l e v e l s of 4d 5s , 4d 6s, 4d y5d and 4d J7s. Some of the terms of 4d 96p, 4d 96d, 4d 94f, and 4d8Ss'5p are also included. The i o n i s a t i o n p o t e n t i a l i s calculated from the 4d 9ns s e r i e s . The term system i s based on the parent of 4d 9 which has a doublet separation of 7171 Cm\"\"* as observed i n InV.The addition of the outer electron 1 w i l l give terms i n two groups with the parent separation of 7171 Cm *., i t w i l l be more so f o r the higher members approaching the jj coupling For such cases i t may seem t h e o r e t i c a l l y wrong to use the notation of L.S coupling but for the sake of s i m p l i c i t y and comparison within the i s o e l e c t r o n i c sequence we are A r e t a i n i n g these. 4d 95p Configuration: As stated before we have only confirmed t h i s system of terms from t h i s configuration. In Table No.8 are compared the t h e o r e t i c a l valu.es calculated byMehlhorn against the experimental values. Parameters Calculated by Mehlhorn Gx - 7762.6 G 3 = 2764.6 -2340.1 F 2 - 22467.5 F Q = 209653.7 46 Tabic No.8 (Comparison of calculated and observed values for terms of 4d 5p) Term Calc. Obs. At,-* Term Calc. Obs. A \u00a3 3 p 193844. 6 193894. 5 -50* F 2 205518. 3 205251.2 267.1 \\ 197121. 8 196599. 0 522* 204947. 2 205849.4 -902.2 200567. 2 200553. 8 13* 208714. 5 208598.3 116. 2 V 201984. 204625. 6 2 201054. 204947. 3 6 930* 5b -312* at; ' \\ 209583. 211136. 1 6 209781.0 21154.6. 9 - 197.9 - 410.3 3\"2 201294. 7 202024. 8 -730* * * 1 D 2 213438. 4 212679.3 759.1 R.M.S error i s calculated to be = 759 Cm~l where mean error i s given by the following r e l a t i o n : R.M.S Error = j \\ (AEj^ ) 2 \/ (n-m) V where A \u00a3 == Observed Energy - Calculated Energy n = Number of energies and m = Number of parameters involved. 47 4 d^ns Configuration: This configuration can be calculated on the b a s i s ( 31) of Houston's theory of intermediate coupling for two electron system when one of the electrons i s an s-electron. The e l e c t r o s t a t i c i n t e r a c t i o n i s given b y , Fo ~ G{ The matrix of : \u00a3 .s i n t e r a c t i o n for J = 2 3 U filt+0 which gives us the secular determinant: W - ( F Q - Gg ) + = 0 48 Solution of t h i s determinent gives the energy values fo r the terms of J = t 1 \/ 4 % ) 2 + l\/ltCi+OU W f o r J = 1 i s s t r a i g h t forward because the spin o r b i t i n t e r a c t i o n i s only 1 x 1 matrix, so that V.j, = !\u2022'\u201e - C. - 1\/2 ( f H 1 ) 3 8 3 5 . 8 6 5 71 138 11 C L A o S I F I ED 2 6 0 7 9 . 6 3 8 3 4 . 4 1 5 199 1 9 0 * 2 6 0 9 6 . 2 3 6 3 1 . 9 7 6 717 11 C L A S o I F I ED 2 6 1 2 6 . 4 3b2 I \u2022 3 4 b 6 8 9 I I I 111 5P@ 2 D 3 \/ 2 * - . 10S 2 S 1 \/ 2 2 6 1 3 0 . 7 3 8 2 6 . 9 1 6 465 IV I V 6S 3D3 - 6P 4* 2 6 2 6 2 . 6 3 8 0 7 . 6 9 6 512 2 6 2 7 2 . 4 3 8 0 6 . 2 7 6 721 2 6 2 8 4 . 4 3 8 0 4 . 3 3 8 227 4 3 8 * IV 2 6 3 1 3 . 0 3 8 0 0 . 4 0 3 365 11 C L A S S I F I E D 2 6 3 1 9 . 0 3 7 9 9 . 3 3 6 753 2 6 3 2 6 . 7 3 7 9 6 . 4 2 5 848 2 6 3 3 6 . 0 3 7 9 7 . 0 6 4 376 2 6 3 4 0 . 8 3 7 9 6 . ^ 9 2 120 221 11 C L A S S I F I E D 2 6 3 9 3 . i 3 7 6 o . 8 o 9 746 371 111 5P@ 2 D 3 \/ 2 * - 9D 2D3\/2 2 6 4 0 2 . 3 3 7 8 7 . 5 4 9 860 7 9 3 * IV 2 6 7 6 7 . 0 3 7 3 5 . 9 4 4 4 7 5 IV 5S2 1D2 - 5P@ 1 0 * 2 6 8 7 3 . 6 3 7 2 1 . 1 2 4 538 6 8 0 * IV 2 6 8 8 2 . 9 3 7 1 9 . 6 3 7 4 2 9 530 11 C L A S S I F I E D 2 6 9 0 0 . 7 3 7 1 7 . 3 75 169 307 11 C L A S S I F I E D 2 6 9 5 8 . 9 3 7 0 9 . 3 5 0 799 11 C L A S S I F I E D 2 6 9 5 0 . 6 3 7 1 0 . 4 9 3 401 IV I V 5S2 3P2 - 6P 3* 2 6 9 6 1 . 6 3 7 0 o . V 7 9 742 11 C L A S S 1 F I ED 2 7 0 6 2 . 4 3 69 5 \u2022 i o 4 309 516 11 C L A S S I F I E D 27411.4 3648.117 655 IV IV 5D 3G4 - 6P 4* 27462.5 3641.316 809 I I I IV 5S2 3P2 -6P 4* 27556.8 3628.868 889 11 C L A S S I F I ED 27576.4 3G2o.2b9 896 27843.2 3591.541 772 IV 5D 3D2 - 5P@ 10* 2 7 8 7 3 . 1 3587.688 730 I V 5D 1D2 - 5P@ 12* 28063.3 3563.373 821 111 4F 2 F 5 \/ 2 * \u2014 7 D 2D3\/2 28152.8 3552.045 730 601 111 4F 2 F 7 \/ 2 * \u2014 7 D 2D5\/2 27924.6 3581.072 873 IV I V 5D 3F3 -6P 7* 28654.4 3489.665 902 IV I V 5D 1D2 - 5P@ 1 3 * 28673.5 3487.541 625 IV IV 5D 3D3 - 6P~ 8* 29024.4 3445.377 654 7 0 6 * 111 29029.2 3444.807 876 29073.1 3439.60o 790 I V 111 5F 2 F 7 \/ 2 * \u2014 9 G 2G 29199.8 3424.681 917 29513.1 338b.326 738 IV IV 582 3P1 - 6P 9* 29606.6 3377.602 848 11 C L A R I F I E D 29679.2 3369.363 857 5 6 0 * IV 6S 3D2 - 6P 7* 29945.0 3339.456 329 506 11 CLASS I F I ED 30307.4 3299.524 ^86 6 0 2 * IV IV 6S 3D3 - 6P 7* 30353.5 3294.513 548 536 IV I I.I 5S2 2D5\/2 - 6P 2 P 3 \/ 2 * 30453.8 3263.6t> 9 8 510 31897.0 3135.091 0 IV 31906.6 3134.148 514 31936.3 313 1.233 500 31985.9 3126.378 960 32225.8 3103.104 414 32250.5 3100.727 328 612 11 C L A S S I F I E D 32392.9 3087.096 177 32421.0 3084.421 5 319 11 C L A S S I F I E D 32424. b 3084.173 540 565 IV 5 D 3P2 - 6P 7* 32446.0 3032.044 756 I I I 3 2 4 7 3 . ^ 3079.462 3 o l 3 2 3 9 8 . i 306 7.bo3 630 I I I C L A S S I F I E D 32606.3 3066.892 967 785 I I I IV 5D 1P1 - 5P@ 1 2 * 32708.9 3057.272 250 IV I V 5D 3F2 - 5P@ 15* 32 733.3 3053.127 966 I I C L A S S I F I E D 32801.1 3046.678 709 I C L A S S I F I E D 32809.2 3047.926 605 I I I 3291 6 . 1 3036.0^7 454 I I I 32949.1 3034.964 378 678 32954.2 3034.515 849 33041.3 3026.497 776 I I 33073.0 3023.6 14 956 I I C L A S S I F I ED 3^226.6 300 9 . OJ>7 232 I I I 1 I I 5D 2D5\/2 - 4F 2 F 5 \/ 2 * 33234.3 3006.940 192 I I I I I I 5D 2D5\/2 -4F 2 F 7 \/ 2 * 33329.0 3000.39U 843 647 I V 6S 1D2 - 4F 14* 33406.5 2993.429 948 I I 33454.9 2989.099 448 I V 6S 3D2 - 5P@ 10* 33466.0 296 7.9 29 706 711 I I I IV 5D 3F2 - 4F 16* 33514.9 2983.748 203 I I I 111 5D 2D3\/2 -4F 2 F 5 \/ 2 * 33530.3 2982.377 767 33556.2 2980.075 743 I I I 33578.7 2978.078 948 33703.3 2967.069 953 I V 50 3F2 - 4F 1 7 * 33808.4 2957.645 439 I C L A S S I F I E D 33354.7 2953.8 00 965 3 4 0 0 0 . 0 2 9 4 1 . 1 lb 561 389 34011.3 2940.199 505 I I I 111 5D 2D5\/2 -5P@ 4 P 5 \/ 2 * 34016.0 2939.793 5 39 623 I-1 I I V 5D 3F2 -5P@ 19* 34024.2 2 9 3 9.085 407 620 I I I I V 6S 3D1 - 5P@ 15* 34112.7 2931.460 846 741 34146.3 2926.575 729 606 I I I IV 6S 1D2 - 4F 16* 34273.0 2917.749 919 I I I 34288.2 2916.455 962 34302.9 5D 2D3\/2 -7P@24P5\/2* 34317.6 2913.957 669 I I I 34382.6 2908.448 822 908 IV 6S 1D2 - 4F 17* 34447.2 2902.994 956 903 I I I I V 5D 1D2 - 5P@ 2 3 * 3 446 6.9 2901.334 486 570 I I I 34543.0 2694.943 684 I I I IV 5S2 3P0 - 5P@ 12* 34646\u20222 2866.3 19 980 603 34648.0 2886.169 982 722 34669.0 2834.421 994 801 I I I 34738.3 2878.667 6 6 6 I I I I V 6S 1D2 - 4F 2 0 * 34783.0 2874.968 984 925 5S2 3P1 - 5P 12* 34837.6 2870 .462 870 670 I I I 34887.4 2866 \u2022 3 64 957 890 IV 50 3D2 - 4F 14* 34913.7 2664, .205 993 I I I 34942.6 2661 . 6 3 0 961 34946.6 2661. .209 829 8 8 1 * I I I I V 5D 3D2 - 5P@ 1 5 * 35002.4 2o56 \u2022 947 712 I I I 35064.3 2851. .904 926 698 I I I 35076.0 2850 .9 3 2 678 I I 35104.3 284o .654 722 I I 35180.4 2842 .492 921 I I I 35206.8 2840 .360 753 588 I I -3 5239.0 2837. .765 449 I C L A S S I F I E D 35231.0 2838. ,409 962 660 3 5 2 9 0 . i 2633. .6 56 929 478 I I I 3 5 4 5 6 . o 2820. .35 7 9o0 I I CLAoi> 1 F I ED 35466.5 2817, 814 776 533 35567.1 2811. .567 807 841 I I I I V 5S2 3P1 - 5P@ 13* 35881.3 z78o. ,96 7 556 368 I I I 35887.0 2 786. , 524 455 I 1 I 35897.2 27 ab. ,733 673 I I I 3:?9i7.4 2 7 8 4. , l o 6 965 65 1 I I I 36043.1 2774, 456 877 5 5 5 ^ I I I 36 3 17.0 2753. .531 781 11 C L A o S I F I E D 36356.5 2750, 540 414 111 5P@ 4D5\/2* \u2014 8 G 2G 36393.0 2747. ,781 142 I I I IV 5D 3F2 - 5P@ 2 2 * 36410.1 2746. .491 401 I I I 36468.0 2742, ,130 661 I I I 36 4 71.7 2 741. 652 908 591 I 1 I 36482.0 2741. 0 76 716 I I I 36492.2 2740. 312 167 423 36672.0 2726. 6 76 157 I I I 111 4F 2 F 7 \/ 2 * \u2014 6 G 2G 36680.2 2726. 266 167 I I I 111 4F 2 F 5 \/ 2 * \u2014 6 G 2G 36810.8 2716. 594 453 722 I I I 36816.2 2716. 196 730 36819.0 2715. 989 605 36843.1 2714. 212 928 37047.0 2699. 274 912 I I I 37074.3 2697. 28t> 622 717 I I I 37100.2 2695. 403 719 816 I I I 3 7245.0 2664. 924 816 11 C L A o S I F I E D 37250.6 2683. 930 841 718 I V 6S 1D2 - 5P@23* 37317.5 2679. 700 896 833 I I I IV 5D 3F2 - 5P@ 2 5 * 37343.3 2677. 857 601 722 I I I 3 7 3 7 7 . 6 2675. 399 420 11 C L A S S I F I E D 37460.2 2 6 6 9 . 500 450 11 C L A o S l F I ED 37514.6 2665. .629 333 903 ) I I I 37577.7 2661, .133 504 678 I I I 37803.0 2645. ,293 626 928 I I I IV 552 3P2 - 4F 1 1 * 38076.1 2626. .161 255 I I I 111 5P@ 4 P 5 \/ 2 * - 8L) 2D5\/2 38113.6 2623. .735 556 I I I I V 5D 3S1 - 6P 9* 3638 5.6 2605. . 130 060 742 I I I I V 65 1D2 - 5P@26* 38424.2 2602, o 2 7 866 I C L A o S l F I E D 38513.6 2 5 9 6 , ,4 72 765 I I I I V 552 3P1 ~ 4F 18* 38569.6 2 5 9 2 . ,716 671 11 C L A o o I F I E u 38667.7 2566, 136 722 I V 65 3D2 5P@ 1 3 * 38794.0 2 577, 6o5 471 I I I I V 5S2 3P1 - 5P@ 19* 38376.9 2572, ,222 663 11 C L A S S I F I E D 39199.2 2551, ,072 530 I I 39227.4 2 5 4 9 . ,239 616 IV 65 1D2 - 5P@27* 39266.0 254o, ,7 33 919 I I I 111 5D 5D 2D3\/2 - 5P(? 4 F 5 \/ 2 * 39269.5 2546. .306 653 11 C L A S S I F I E D 3 9 3 1 1 . 4 - Vw Vo V. 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