RADITIVE CONSTANTS OF HgI, HgII and HgIII SPECTRA

Kiril Blagoev

Institute of Solid State Physics, Sofia, BULGARIA

•Introduction

•Radiative Constants of Hg I States

•Radiative Constants of Hg II States

•Radiative Constants of Hg III States

•Conclusion

()

I(t)

tAki

Akb

Aka

fik b

a

k

i

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/Aik

Aik = (1/i)(Ii/Ij)

Delaygenerator

Helmholtzcoil

Topview

Ablation laser

Nd:YAGlaser (A)

Rotating Zr target

MCPPMT

Monochromator

TransientDigitizer

Computer

Trigger

KDP BBO

Sideview

Trigger

Nd:YAGlaser (B)

SBScompressor

Dyelaser

Lund Laser Centre – Time Resolved Laser Induced Fluorescence Equipment

0 4 8 12 16 20 24 280

200

400

600

800

1000

Inte

nsity (

Arb

. U

nits)

Time (ns)

Signal Fit Laser pulse

LIF Signal from ZrIII Excited State

MONOCHROMATORElectron gun

Vacuum system

Generator Time - to - Amplitude Converter

Amplifier

Amplitude Analyzer

PMT

Start Stop

t1

t2

Experimental set-up for delayed coincidence method – electron

excitation

0 100 200 300 400 500

10

100

1000

Ee=70eV, N

hg=2.9

.10

14cm

-3

794.4 nm(7p2P

1/2 - 7s

2S

1/2)

HgII 7p2P

1/2

0.781ns/channel

I(t)

channel

Deacay curve of the HgII 7p2P1/2 state

Madrid University – LIBS Equipment

0 200 400 600 800 1000 1200

0

10000

20000

30000

40000

268.119 AgII266.050 AgII

261.438 AgII

500 ns

300 ns

200 ns

100 ns

270.7260.3

Rela

tive inte

nsitie

s (

arb

. u.)

Wavelengths (nm)

LIBS Spectrum of Ag II

1D

2

3P

2

3F

4

Hg+

3D

3

1P

1

185

0

126

9

99

E (

x 10-3

cm

-1)

5d10

6p2

8

8

8

8

7

67

77

7

7

6

6

6

6

6

HgI 5d10

6s2 1S

0

3D

3

3D

2

3D

1

3P

2

3P

1

3P

0

3S

1

5d96s

26p'

1S

0

1P

1

1D

2

0

30

40

50

60

70

80

Grotrian diagram of HgI

  Experiment Theory

State [1]LIF

[2] e-ph

[3] =1/Aik

[4] BF

[5]BF

[6]

6p1P 1.3 1.35 1.27 1.2

7p1P 26 12

8p1P 72 38

9p1P 10 10

10p1P 55.6 51 41

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 np1P states of HgI(ns).

Table 2. Radiative Lifetimes of n3P states of HgI(ns).

Experiment Theory

State [1] DC 2002

[2] Hanle, 1975

[3] , =1/Aik

1987

[4]

8p3P0 248 213

8p3P1 167 61 42 177

8p3P2 156 95 145

9p3P0 339

9p3P1 135 79 124

9p3P2 41

10p3P2 375 44

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)

Table . Radiative lifetimes of Beutler states of HgI (ns)

State Transition , nm [1] DC

[2] Hanle

[3] = 1/Aik

5d96s26p 1D2 6p’1D2 - 7s3S1 612.3 1480 1600

5d96s26p 1P1 6p’1P1 - 7s1S0 671.6 5.3 4.5

5d96s26p 3P2 6p’3P2 - 7s3S1 1529.5 160

5d96s26p 3F4 6p’3F4 - 6d3D3 1813.0 450

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)

Transition nm [1] [2] [3]  [4]  [5]

    1989 1978 1980    

63P1-61S 253.6 0.08 - 0.13  0.08  0.083

61P1-61S 184.9 - -    1.9  7.6

73S1-63P0 404.6 0.208 0.186 0.18 0.21   

73S1-63P1 435.8 0.558 0.424 0.4 0.56   

73S1-63P2 546.0 0.485 0.595 0.56  0.49  

71S1-63P1 407.8 0.041 0.043 0.041  0.04  

71S1-61P1 1014.2 0.271 0.283 -  -  

63D1-63P0 296.7 - 0.477 0.45  0.85  

63D1-63P1 313.3 - - -  0.0063  

63D1-63P2 366.3 - - -  0.046  

63D1-61P1 578.9 - - -  0.42  

63D2-63P1 312.6 0.65 0.532 0.51  0.66  

63D2-63P2 365.5 0.184 - -  0.18  

63D2-61P1 576.9 - - -  0.24  

63D3-63P2 365.0 1.28 - -  1.3  

5d96s26p’1P1-61S 126.8 9.2 2.1

Table Transition probabilities in HgI (108 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)

•Introduction

•Radiative Constants of Hg I States

•Radiative Constants of Hg II States

•Radiative Constants of Hg III States

•Conclusion

Grotrian Diagram of HgII - 5d10nl States

Grotrian Diagram of HgII – 5d10nl and 5d96s6p States

Table Radiative Lifetimes of 5d10nl States of Hg II (ns)

State, Å Transition [1] DC

1988.[2] BF1976

[3] BF 1988

[4] BF1993

[4] Theory1993

7s2S1/2 7s2S1/2 – 6p2P3/2 1.99

6p2P1/2 1942.3 6p2P1/2 – 6s2S1/2 2.91

6p2P3/2 1649.9 6p2P3/2 – 6s2S1/2 1.80

7p2P1/2 7944.5 7p2P1/2 – 6s2S1/2 18.8(12)

14.5 2.05HF,22.86c

7p2P3/2 6149.5 7p2P3/2 – 6s2S1/2 3.1(2) 1.2 3.12HF,2.17c

6d2D3/2 1869.4 6d2D3/2 – 6p2P1/2 1.15

6d2D5/2 2224.7 6d2D5/2 – 6p2P3/2 1.9 1.56

5f2F5/2 5425.2 5f2F5/2 – 6d2D3/2 3.2(2) 2.7

5f2F7/2 5677.2 5f2F7/2 – 6d2D5/2 8.6(9) 7.6

6g2G 6291.3 6g2G - 5f2F7/2 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)

1.45 1.50 1.55 1.60 1.65 1.70 1.75 1.80 1.85 1.90 1.95 2.00

0.0

0.5

1.0

1.5

2.0

2.5

3.0

*ns

2S

1/2

np2P

3/2

nd2D

3/2

nd2D

5/2

ln()

ln(n*)

0.9 1.0 1.1 1.2 1.3 1.4 1.5 1.6

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

=6.6

=3.06

nf2F

7/2nf2F

5/2

ng2G

ln()

ln(n*)

Dependence of radiative Lifetimes vs effective principal quantum number (n*) for ns2S, np2P, nd2D, nf2F and ng2G series of HgII.

K. B. Blagoev et al Phys. Rev A13,4683(1988);

State nm

Transition [1] DC [2] ion trap 1990

[3] Theory 19991984,1986

5d96s2 2D3/2 198.0 2D3/2 - 2S1/2   8.8ms  

5d96s2 2D5/2 281.5 2D5/2 - 2S1/2   87ms 69.8ms

5d96s6p(J=9/2)       60ms 97.4ms

5d96s6p 15/20 226.2 15/2

0 - 2D5/21 250(6)    

5d96s6p 21/20 205.3 21/2

0 - 2D5/21 39(1.5)    

5d96s6p 35/20 291.6 35/2

0 - 2D3/21 150(6)    

5d96s6p 105/20 214.8 105/2

0 - 2D3/21 46(3)    

2D3/23 448.7 2D3/2

3 - 15/20 10(0.5)    

2D5/2 363.8 2D5/2 - 15/20 6.0(0.6)    

2D7/22 295.7 2D7/2

2 - 4P5/2 27(2)    

4D1/22 300.4 4D1/2 - 43/2

0 5.0(0.5)    

4D7/23 347.3 4D7/2

3 - 54P5/2 4.3(0.4)    

5d96s7s45/2 240.7 45/2 - 77/20 3.2(0.4)    

5d96s7s55/2 354.9 55/2 - 243/20 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 5d96s6p States of HgII

Transition ,nm [1]Theory

[2]Theory

[3] Theory

[4]BF-ANDC

[5]LIF

6p2P1/2 – 6s2S1/2 194.2 5.3 7.5 3.44 3.8

6p2P3/2 – 6s2S1/2 165.0 8.5 12 5.56

7p2P1/2 – 6s2S1/2 92.33 - 6.5 0.006

7p2P3/2 – 6s2S1/2 89.30 - 0.575 1.076

7p2P1/2 – 7s2S1/2 794.4 0.47 0.43 0.395

7p2P3/2 – 7s2S1/2 614.9 0.87 0.7 0.453

6d2D3/2 - 6p2P1/2 186.9 7.5 10.5

6d2D3/2 - 6p2P3/2 225.3 1.2 1.2

6d2D5/2 - 6p2P3/2 222.5 7.1 7.5 6.4

7s2S1/2 - 6p2P1/2 226.0 1.3 3.0

7s2S1/2 - 6p2P3/2 284.8 2.3 2.95 5.03

Table Transition Probabilities in Hg II spectrum (108 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)

•Introduction

•Radiative Constants of Hg I States

•Radiative Constants of Hg II States

•Radiative Constants of Hg III States

•Conclusion

Grotrian Diagram of Hg III

State Transition ,Å ,Exper. ,Theory Aik,Exper. Aik,Theory

112 (3P2) 112-12

o(3P2) 6501 2480(120) 1250 3.55 7.0

112-23o(3F3) 7517 0.48 1.0

101 (3P1) 101-12

o(3P2) 5210 1660(100) 600 6.00 16.0

101-41o(3P1) - 0.8

124 (1G4)

124-20o(3F3) 4797 2100(130) 580 4.76 17.0

132 (1D2)

132-12o(3P2) 3312 2250(150) 760 2.43 4.0

132-23o(3F3) 3557 1.62 1.0

132-32o(1D2) 6584 0.26 -

132-41o(3P1) 6610 0.13 -

132-81o(1P1) - - 4.0

132-62o(3F2) 7808 0.20

140 (1S0) 140-81

o(1P1) 3090 473(20) 120 20.6

140-111o(3D1) 4181 0.2 -

140-41o(3P1) 2480 - 0.02

Table Radiative lifetimes (ns) and transition probabilities(105s-1) in HgIII

K. Blagoev et al Phys. Lett A117, 185(1986); A118,232(1986)

State E, cm-1 Transition ,Å ,exp. ,theory

5d96p3D1 134998 5d96p3D1-5d10 1S0

740.75 0.90 0.70;0.63

5d96p1P1 126556 5d96p 1P1-5d10 1S0

790.17 0.52 0.28;0.26

5d96p 3P1 118607 5d96p 3P1-5d10 1S0

843.11 1.20 1.00;0.88

Table Radiative Lifetimes of 5d96p states of HgIII(ns)

D. J. Beideck et al Phys. Rev. A47, 884(1993)

50 100 150 200 250 300 3500.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

479.7nm

331.2nm

Qki,1

0-18 cm

2

E,eV

Excitation functions of HgIII 5d86s2 – 5d96p spectral lines

50 100 150 200 250 300 3500.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

479.7nm

331.2nm

Qki,1

0-18 c

m2

E,eV

Excitation functions of HgIII 5d86s2 – 5d96p spectral lines

HgI(5d106s2) + e (Hg2+) 5d86s2 + 3e,

HgI(5p65d106s2 ) + e (Hg+)** (5p55d10 6s2 ) + 2e (Hg2+)*5d65d86s2 +3e “ionization” “autoionization”

(Hg+)** 5p55d106s2, 72 eV

E,eV

Hg2+ 5d86s2, 1G4 (44.7 eV)

Hg2+5d96p 3F3

4797Å

Hg2+ 5d10 1S0 -18.7eV eV

Hg+ 5d106s 2S1/2 10.4eV

Hg I 5d106s2 1S0

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“.

State Experiment Theory

  [1]LIF [2]LIF [3]LIF [ 4]LIF [5]BF [6]LIF [1]1999

[2]2002

[7]19781999 2002 1980 1989 1988 1986

6d1D2     10.9   14 10.6 8   17

3D1   6.8     6   4 5.6 6.9

3D2       9.3 8.8 9.2 7   7

3D3       7.8 6.8   8   7.9

7d1D2 38.3   40 34.9   37 37   50

3D1   17         11 14 16

3D2 17.3     18.1   17 16   17

3D3       18.2     20   18

8d1D2 122   126       82    

3D1   32         24 32  

3D2 35.8           31    

3D3             38    

91D2             144    

3D1   56         47 48  

3D2 55           59    

10d3D1   84           88  

3D2 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)

Table 1. Radiative Lifetimes of ns States of HgI (ns).

State Experiment Theory

[1]LIF2002

[2]e-ph1975

[3]LIF1980

[4]LIF1989

[1]2002

[5]1978

7s1S 31.0 30.3 3S 8.0 7.7 8.0 7.4 8.4

8s1S 84 63 3S 24.2 22.1 20 21

9s 1S 142 3S 53 22 39

10s1S 3S 92 52

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)

State E, cm-1 Transition ,Å Qik Qi

112 118926 112 – 12o 6501 0.14 0.16

122735 112 – 23o 7517 0.02

101 126468 101 - 12o 5210 0.18 0.18

124 133731 124 - 23o 4797 1.30 1.30

132 132 - 12o 3312 0.19 0.35

132 - 23o 3557 0.12

132 – 32o 6584 0.03

132 – 41o 6610 0.01

132 – 62o 7808 0.02

140 158909 140 - 81o 3090 0.14 0.14

Table Electron impact cross sections for 5d86s2 States of HgIII(10-18cm2)

K. Blagoev et al Phys. Lett A118,232(1986)