1. RADITIVE CONSTANTS OF HgI, HgII and HgIII SPECTRA Kiril Blagoev Institute of Solid State Physics, Sofia, BULGARIA

2. Introduction Radiative Constants of Hg I States Radiative Constants of Hg II States Radiative Constants of Hg III States Conclusion

3. Experimental methods for lifetime and transition probabilities determination 1.Lifetimes - time evolution of the population + Beam foil/laser + time resolved method ++ electron excitation ++ laser excitation ( LIF) -Width of the excited states + Hanle method Transition probabilities – Branching ratio  I = 1/  A ik A ik = (1/  i )(I i /  I j )

4. Delay generator Helmholtz coil Top view Ablation laser Nd:YAG laser (A) Rotating Zr target MCP PMT Monochromator Transient Digitizer Computer Trigger KDP BBO Side view Trigger Nd:YAG laser (B) SBS compressor Dye laser Lund Laser Centre – Time Resolved Laser Induced Fluorescence Equipment

5. LIF Signal from ZrIII Excited State

6. MONOCHROMATOR Electron gun Vacuum system GeneratorTime - to - Amplitude Converter Amplifier Amplitude Analyzer PMT StartStop t1t1 t2t2 Experimental set-up for delayed coincidence method – electron excitation

7. Deacay curve of the HgII 7p 2 P 1/2 state

8. Madrid University – LIBS Equipment

9. LIBS Spectrum of Ag II

10. Grotrian diagram of HgI

11. ExperimentTheory State[1] LIF [2] e-ph [3]  =1/  Aik [4] BF [5] BF [6] 6p 1 P1.31.351.271.2 7p 1 P2612 8p 1 P7238 9p 1 P10 10p 1 P55.65141 1. K. Blagoev et al proc. SPIE, v. 5256,164(2002); 2. G. C. King et al J. Phys. B B8, 365(1975); 3. W. J. Alford et al Phys. Rev A36, 641(1987); 4. E. H. Pinnington et al Canadian J of Physics, 66, 960(1988); 5. T. Anderson et al JQSRT 13,369(1973); 6. P. Hafner et al J. Phys. B 11, 2975(1978) Table 1. Radiative Lifetimes of np 1 P states of HgI(ns).

12. Table 2. Radiative Lifetimes of n 3 P states of HgI(ns). ExperimentTheory State[1] DC 2002 [2] Hanle, 1975 [3],  =1/  A ik 1987 [4] 8p 3 P 0 248213 8p 3 P 1 1676142177 8p 3 P 2 15695145 9p 3 P 0 339 9p 3 P 1 13579124 9p 3 P 2 41 10p 3 P 2 37544 1. K. Blagoev et al Proc SPIE,v5226, 164(2002), Proc. EGAS34,186(2002) 2. E. Alipieva et al Opt. Sprctr. 43,529(1977); 3. W. J. Alford et al Phys. Rev A36, 641(1987); 4. P. Hafner et al J. Phys. B 11, 2975(1978)

13. Table. Radiative lifetimes of Beutler states of HgI (ns) StateTransition, nm [1] DC [2] Hanle [3]  = 1/  A ik 5d 9 6s 2 6p 1 D 2 6p’ 1 D 2 - 7s 3 S 1 612.314801600 5d 9 6s 2 6p 1 P 1 6p’ 1 P 1 - 7s 1 S 0 671.65.34.5 5d 9 6s 2 6p 3 P 2 6p’ 3 P 2 - 7s 3 S 1 1529.5160 5d 9 6s 2 6p 3 F 4 6p’ 3 F 4 - 6d 3 D 3 1813.0450 1.K.Blagoev et al Proc. SPIE, v4397, p. 256(20010; 2. G. Goullet et al, C. R. Acad. Paris 259, 93(1964); 3. W. J. Alford et al Phys. Rev A36, 641(1987)

14. Transition nm [1][2][3] [4] [5] 198919781980 6 3 P 1 -6 1 S253.60.08-0.13 0.08 0.083 6 1 P 1 -6 1 S184.9-- 1.9 7.6 7 3 S 1 -6 3 P 0 404.60.2080.1860.180.21 7 3 S 1 -6 3 P 1 435.80.5580.4240.40.56 7 3 S 1 -6 3 P 2 546.00.4850.5950.56 0.49 7 1 S 1 -6 3 P 1 407.80.0410.0430.041 0.04 7 1 S 1 -6 1 P 1 1014.20.2710.283- - 6 3 D 1 -6 3 P 0 296.7-0.4770.45 0.85 6 3 D 1 -6 3 P 1 313.3--- 0.0063 6 3 D 1 -6 3 P 2 366.3--- 0.046 6 3 D 1 -6 1 P 1 578.9--- 0.42 6 3 D 2 -6 3 P 1 312.60.650.5320.51 0.66 6 3 D 2 -6 3 P 2 365.50.184-- 0.18 6 3 D 2 -6 1 P 1 576.9--- 0.24 6 3 D 3 -6 3 P 2 365.01.28-- 1.3 5d 9 6s 2 6p’ 1 P 1- 6 1 S 126.89.22.1 Table Transition probabilities in HgI (10 8 s -1 ). 1. E. C. Benck et al, JOSA B6(1), 11(1989) 2. E. R. Mosburg et al, J. Q. S. R. T. 19, 69(1978) 3. W. L. Wiese and G. A. Martin, Wavelengths and transition probabilities for atoms and atomic ions Part II(NIST -1980) 4. R. Payling et al Optical Emission Lines of the Elements (John Wiley&Son LTD, 2000) 5. A. Smith et al Phys. Rev,A33, 3172(1986)

15. Introduction Radiative Constants of Hg I States Radiative Constants of Hg II States Radiative Constants of Hg III States Conclusion

16. Grotrian Diagram of HgII - 5d 10 nl States

17. Grotrian Diagram of HgII – 5d 10 nl and 5d 9 6s6p States

18. Table Radiative Lifetimes of 5d 10 nl States of Hg II (ns) State, Å Transition [1] DC 1988. [2] BF 1976 [3] BF 1988 [4] BF 1993 [4] Theory 1993 7s 2 S 1/2 7s 2 S 1/2 – 6p 2 P 3/2 1.99 6p 2 P 1/2 1942.36p 2 P 1/2 – 6s 2 S 1/2 2.91 6p 2 P 3/2 1649.96p 2 P 3/2 – 6s 2 S 1/2 1.80 7p 2 P 1/2 7944.57p 2 P 1/2 – 6s 2 S 1/2 18.8(12)14.52.05 HF,22.86 c 7p 2 P 3/2 6149.57p 2 P 3/2 – 6s 2 S 1/2 3.1(2)1.23.12 HF,2.17 c 6d 2 D 3/2 1869.46d 2 D 3/2 – 6p 2 P 1/2 1.15 6d 2 D 5/2 2224.76d 2 D 5/2 – 6p 2 P 3/2 1.91.56 5f 2 F 5/2 5425.25f 2 F 5/2 – 6d 2 D 3/2 3.2(2)2.7 5f 2 F 7/2 5677.25f 2 F 7/2 – 6d 2 D 5/2 8.6(9)7.6 6g 2 G6291.36g 2 G - 5f 2 F 7/2 26.8(20) 1. K. B. Blagoev et al Phys. Rev A13,4683(1988); 2. T. Anderson et al, JQSRT 16, 521(1976); 3. E. H. Pinnington et al Canadian J of Physics, 66, 960(1988); 4. S. J. Maniak et al Phys. Lett. A182, 114(1993)

19. Dependence of radiative Lifetimes vs effective principal quantum number (n*) for ns 2 S, np 2 P, nd 2 D, nf 2 F and ng 2 G series of HgII. K. B. Blagoev et al Phys. Rev A13,4683(1988);

20. State    nm Transition [1] DC [2] ion trap 1990 [3] Theory 1999 1984,1986 5d 9 6s 2 2 D 3/2 198.0 2 D 3/2 - 2 S 1/2 8.8ms 5d 9 6s 2 2 D 5/2 281.5 2 D 5/2 - 2 S 1/2 87ms69.8ms 5d 9 6s6p(J=9/2) 60ms97.4ms 5d 9 6s6p 1 5/2 0 226.21 5/2 0 - 2 D 5/2 1 250(6) 5d 9 6s6p 2 1/2 0 205.32 1/2 0 - 2 D 5/2 1 39(1.5) 5d 9 6s6p 3 5/2 0 291.63 5/2 0 - 2 D 3/2 1 150(6) 5d 9 6s6p 10 5/2 0 214.810 5/2 0 - 2 D 3/2 1 46(3) 2 D 3/2 3 448.7 2 D 3/2 3 - 1 5/2 0 10(0.5) 2 D 5/2 363.8 2 D 5/2 - 1 5/2 0 6.0(0.6) 2 D 7/2 2 295.7 2 D 7/2 2 - 4 P 5/2 27(2) 4 D 1/2 2 300.4 4 D 1/2 - 4 3/2 0 5.0(0.5) 4 D 7/2 3 347.3 4 D 7/2 3 - 5 4 P 5/2 4.3(0.4) 5d 9 6s7s4 5/2 240.74 5/2 - 7 7/2 0 3.2(0.4) 5d 9 6s7s5 5/2 354.95 5/2 - 24 3/2 0 3.3(0.3) 1.K. Blagoev et al Phys. Lett A106, 249(1984), A117, 185(1986); 2. A. Calamai et al Phys. Rev A42, 5425(1990) 3. T. Brage et al, The Astrph. J. 513, 524(1999) Table Radiative Lifetimes of 5d 9 6s6p States of HgII

21. Transition,nm [1] Theory [2] Theory [3] Theory [4] BF-ANDC [5] LIF 6p 2 P 1/2 – 6s 2 S 1/2 194.25.37.53.443.8 6p 2 P 3/2 – 6s 2 S 1/2 165.08.5125.56 7p 2 P 1/2 – 6s 2 S 1/2 92.33-6.50.006 7p 2 P 3/2 – 6s 2 S 1/2 89.30-0.5751.076 7p 2 P 1/2 – 7s 2 S 1/2 794.40.470.430.395 7p 2 P 3/2 – 7s 2 S 1/2 614.90.870.70.453 6d 2 D 3/2 - 6p 2 P 1/2 186.97.510.5 6d 2 D 3/2 - 6p 2 P 3/2 225.31.2 6d 2 D 5/2 - 6p 2 P 3/2 222.57.17.56.4 7s 2 S 1/2 - 6p 2 P 1/2 226.01.33.0 7s 2 S 1/2 - 6p 2 P 3/2 284.82.32.95  5.03 Table Transition Probabilities in Hg II spectrum (10 8 sec-1) [1. R. Payling et al Optical Emission Lines of the Elements (John Wiley&Son LTD, 2000); 2. C. Sansonetti and J. Reader Physica Scripta 63,219(2001); 3. J. Migdalek, Can. J. Phys. 54, 2272(1978); 4. E. Pininngton et al, Can. J Phys. 66, 960(1988), 5. W. M. Itano et al, Phys. Rev. A59,2732(1987)

22. Introduction Radiative Constants of Hg I States Radiative Constants of Hg II States Radiative Constants of Hg III States Conclusion

23. Grotrian Diagram of Hg III

24. StateTransition,Å ,Exper. , Theory A ik,Exper.A ik,Theory 11 2 ( 3 P 2 ) 11 2 -1 2 o ( 3 P 2 )65012480(120)12503.557.0 11 2 -2 3 o ( 3 F 3 )75170.481.0 10 1 ( 3 P 1 ) 10 1 -1 2 o ( 3 P 2 )52101660(100)6006.0016.0 10 1 -4 1 o ( 3 P 1 )-0.8 12 4 ( 1 G 4 ) 12 4 -2 0 o ( 3 F 3 )47972100(130)5804.7617.0 13 2 ( 1 D 2 ) 13 2 -1 2 o ( 3 P 2 )33122250(150)7602.434.0 13 2 -2 3 o ( 3 F 3 )35571.621.0 13 2 -3 2 o ( 1 D 2 )65840.26- 13 2 -4 1 o ( 3 P 1 )66100.13- 13 2 -8 1 o ( 1 P 1 )--4.0 13 2 -6 2 o ( 3 F 2 )78080.20 14 0 ( 1 S 0 ) 14 0 -8 1 o ( 1 P 1 )3090473(20)12020.6 14 0 -11 1 o ( 3 D 1 )41810.2- 14 0 -4 1 o ( 3 P 1 )2480-0.02 Table Radiative lifetimes (ns) and transition probabilities(10 5 s -1 ) in HgIII K. Blagoev et al Phys. Lett A117, 185(1986); A118,232(1986)

25. StateE, cm -1 Transition,Å ,exp. ,theory 5d 9 6p 3 D 1 1349985d 9 6p 3 D 1 -5d 10 1 S 0 740.750.900.70;0.63 5d 9 6p 1 P 1 1265565d 9 6p 1 P 1 -5d 10 1 S 0 790.170.520.28;0.26 5d 9 6p 3 P 1 1186075d 9 6p 3 P 1 -5d 10 1 S 0 843.111.201.00;0.88 Table Radiative Lifetimes of 5d 9 6p states of HgIII(ns) D. J. Beideck et al Phys. Rev. A47, 884(1993)

26. Excitation functions of HgIII 5d 8 6s 2 – 5d 9 6p spectral lines

27. HgI(5d 10 6s 2 ) + e  (Hg 2+ ) 5d 8 6s 2 + 3e, HgI(5p 6 5d 10 6s 2 ) + e  (Hg + )** (5p 5 5d 10 6s 2 ) + 2e  (Hg 2+ )*5d 6 5d 8 6s 2 +3e “ionization” “autoionization”

28. (Hg + )** 5p 5 5d 10 6s 2, 72 eV E,eV Hg 2+ 5d 8 6s 2, 1 G 4 (44.7 eV) Hg 2+ 5d 9 6p 3 F 3 4797Å Hg 2+ 5d 10 1 S 0 - 18.7eV eV Hg + 5d 10 6s 2 S 1/2 10.4eV Hg I 5d 10 6s 2 1 S 0

29. CONCLUSION 1.The most accurate values for transition probabilities have been obtained by Branching Ratio and normalising them by excited state lifetimes observed by Laser Induced Fluorescence. 2.One has to be careful when the different sets of data from different papers are used. 3.In some cases, due to the cancellation effects or strong electron configuration mixing the real transition probabilities or radiative lifetimes could differ considerably from calculated one. 4.If there are some difficulties or suspicious of choosing the best set of data it is better to ask colleagues from WG “Fundamental data“.

30. StateExperimentTheory [1]LIF[2]LIF[3]LIF[ 4]LIF[5]BF[6]LIF[1] 1999 [2] 2002 [7] 1978 199920021980198919881986 6d 1 D 2 10.9 1410.68 17 3 D 1 6.8 6 45.66.9 3 D 2 9.38.89.27 7 3 D 3 7.86.8 8 7.9 7d 1 D 2 38.3 4034.9 37 50 3 D 1 17 111416 3 D 2 17.3 18.1 1716 17 3 D 3 18.2 20 18 8d 1 D 2 122 126 82 3 D 1 32 2432 3 D 2 35.8 31 3 D 3 38 91D291D2 144 3 D 1 56 4748 3 D 2 55 59 10d 3 D 1 84 88 3 D 2 59.4 Table Radiative Lifetimes of nd States of HgI(ns ) 1. K. Blagoev et al, Physica Scripta 60,32(1999);E.Phys. J, D13,159(2001); 2. K. Blagoev et al Phys. Rev. A66,032509(2002), 4. E. C. Benck et al, JOSA B6(1), 11(1989), 5. E. Pinnington et al, Can. J Phys. 66, 960(1988); 6. M. Darrach et al, JQSRT 36,483(1986); 7. P. Hafner et al J. Phys. B 11, 2975(1978)

31. Table 1. Radiative Lifetimes of ns States of HgI (ns). StateExperimentTheory [1]LIF 2002 [2]e-ph 1975 [3]LIF 1980 [4]LIF 1989 [1] 2002 [5] 1978 7s 1 S31.030.3 3 S8.07.78.07.48.4 8s 1 S8463 3 S24.222.12021 9s 1 S142 3 S532239 10s 1 S 3 S9252 1. K. Blagoev et al Phys. Rev. A66,032509(2002), 2. G. C. King et al, J. Phys. B8,653(1975); 3. F. Faisol et al J. Phys. B13, 2027(1980); 4. E. C. Benck et al, JOSA B6(1), 11(1989); 5. P. Hafner et al J. Phys. B 11, 2975(1978)

32. StateE, cm -1 Transition,Å Q ik QiQi 11 2 11892611 2 – 1 2 o 65010.140.16 12273511 2 – 2 3 o 75170.02 10 1 12646810 1 - 1 2 o 52100.18 12 4 13373112 4 - 2 3 o 47971.30 13 2 13 2 - 1 2 o 33120.190.35 13 2 - 2 3 o 35570.12 13 2 – 3 2 o 65840.03 13 2 – 4 1 o 66100.01 13 2 – 6 2 o 78080.02 14 0 15890914 0 - 8 1 o 30900.14 Table Electron impact cross sections for 5d 8 6s 2 States of HgIII(10 -18 cm 2 ) K. Blagoev et al Phys. Lett A118,232(1986)