1. DCl (HCl) Heavy Rydberg states work Exploring V state spectra
Content: pages: Mass resolved HCl/DCl spectra……………………………………………… 2-5 Analaysis of cm-1 spectrum (Strange?)…………………… 6-7
Spectra analysis for v´= 21 – 28(?)………………………………………
„overall REMPI spectra“………………………………………………………. 17
Spectra reanalysed (v´= 21-29)……………………………………………
E (and V states), DCl, from the literature……………………………… 25-27
Reanalysis by Wang: effects…………………………………………………
Effect of E state: DE vs E……………………………………………………………
E(v´) and B´values: tables………………………………………………………… 37-38
E(v´) and DE estimates for v´= 8 – 11………………………………………
Effect of E state: B´ vs v´ ………………………………………………………… 41
n(J) vs J(J+1) (Q lines) plot for v´´ = 23………………………………….. 42
Updated results for T´and B´ vs v´(V state)………………………… perturbation vs. deperturbation…………………………………………… HCl energy levels and spacings……………………………………………… 49
Updated (170410) analysis of V(v´) data for DCl…………………… search for realistic J0 value for V(v´=26)……………………………….. 53
Improvement for V(v´)………………………………………………………… V(v´=17 & 18), DE(J,J-1) vs. J…………………………………………………. 62
V(v´=20-28), DE(J,J-1) vs. J (v´= 26??)…………………………………… v´= 26?
Updated table for V(v´)………………………………………………………… 67
Comparisons of DCl and HCl………………………………………………… 68-71
Updated:

2. https://notendur. hi. is/~agust/rannsoknir/rempi/dcl/PXP-161020VHW-AK
; Lay0: PICT_2

3. See slide 5
; Lay1: PICT_3

4. https://notendur. hi. is/~agust/rannsoknir/rempi/dcl/PXP-161020VHW-AK
; Lay2: PICT_4

5. HCl/DCl Possible V state spectrum:
37Cl+ and D35Cl+
H35Cl+
; Gr6, Lay3

6. Based on a rough estimate of 88958
Based on a rough estimate of cm-1 for the band origin (= 2hv value for the hghest wavenumber peak)
and extrapolation of vibrational spacing from that for the v´ = states v´ for the cm-1 band is estimated to be about v´= 27 – 28.
Now we will search the region D(2hv) = cm-1 to look for bands v´ » 21 – 27.

7. The spectrum at 88958.8 cm-1 is not a DCl V state spectrum:
2hv J
2hv
J(J+1)
D(2hv) 1 2 6 3 12 4 20 5 30 42 7 56 8 72 9 90
D35Cl
K0=DT:
D(DT)
K1=DB
D(DB)
K2=DD
D(DD)
B´´(v´´=0)
D´´(v´´=0)
B´(v´)
D´(v´)
88959
2.01
0.129
5.09E-04
J(J+1)
sheet: DCl,V states
; Gr0

8. Important papers: Ref: Authors, Title: v´:
Douglas and Greening, The electronic spectra of HCI and HF v´= (?)
Paul J. Dagdigian et al., Detection of DCl by multiphoton ionization and determination of DCl and HCl internal state distributions v´=
R. Callaghan et al., Resonantly enhanced two-photon spectroscopy of HCl and DCl in the cm-1 region
DAVID S. GREEN, * GRANT A. BICKPL, 3 AND STEPHEN C. WALLACE: (2 + 1) Resonance Enhanced Multiphoton Ionization of Hydrogen Chloride in a Pulsed Supersonic Jet: Vacuum Wavenumbers of Rotational Lines with Detailed Band Analysis for Excited Electronic States of H3%11 DAVID S. GREEN, ’ GRANT A. BICKEL, 3 AND STEPHEN C. WALLACE
J. A. COXON AND P. G. HAJIGEORGIOU : Rotational Analysis of the B ‘IZ+ --) X’Z+ Emission Bands of D35CI
Rohana Liyanagea) and Robert J. Gordon & Robert W. Field, Diabatic analysis of the electronic states of hydrogen chloride; Includes DCl as well
S. G. TILFORD, M. I,. GINTER:Electronic Spectra and Structure of the Hydrogen Halides: States Associated with the (2~‘) CT and (22) ccr Configurations of HCI and DCI

9. :

10. DT = t = T´(v´) –T´´(v´´=0) T´= t + T´´
Analysis :
2hn = DT t
+DB J(J+1) +bJ(J+1)
-DDJ2(J+1) 2 +dJ2(J+1) 2
DT = t = T´(v´) –T´´(v´´=0) T´= t + T´´
DB = b = B´(v´) – B´´(v´´=0) B´= b+B´´
DD = -d = D´(v´) – D´´(v´´=0) D´=-d + D´´

11. V´= 21 V´= 22 reassigned 23 below 2hv 2hv J(J+1) J(J+1)
Lay:0, Gr:0 Lay:1, Gr:1

12. V´= 23 reassigned 24 below V´= 24 reassigned 25 below 2hv
Removed and shifted
2hv
J(J+1)
J(J+1)
Lay:2, Gr:2 Lay:3, Gr:3

13. V´= 25 reassigned 26 below V´= 26 reassigned 27 below 2hv
Removed and shifted
2hv ?
J(J+1)
J(J+1)
Lay:4, Gr:4 Lay:5, Gr:5

14. V´= 27 reassigned 28 below V´= 28 reassigned 29 below 2hv 2hv J(J+1)
Lay:6, Gr:6 Lay:7, Gr7

15. V´= 21 22 23 24 25 26 27 28 wy 2 3 5 6 8 12 14 16 wx 1 4 7 9 13 15 17
Ki´s
Dki´s
K0=t=
86587
0.499
87060
1.31
87408
3.12
87804
0.703
88168
3.32
88569
3.36
88978
0.354
89259
0.437
K1=b=
0.0508
-2.005
0.133
0.249
0.0561
0.448
-2.193
0.139
0.0664
0.122
K2=d=
0.0024
0.0106
B´´
D´´
T´´= T´ B´ D´
ref:
T´(ref.)
B´(ref.)
2.275
D´(ref.)
1.10E-03

16. The above data and analysis needs revision.
In particular the red colored numbers above look strange.
Furthermore an additional V state, assigned v´= 22 was observed (see slide below; red assignment)
Below peaks which initially were asigned to the lowest J´s (J´= 0, 1) have either been removed or shifted ore both

17. 2hv/cm-1
Lay:8, Gr:6

18. D35Cl, V-state V´= 21 V´= 22 2hv 2hv J(J+1) J(J+1)
Lay:0, Gr:0 Lay:8, Gr:9

19. D35Cl, V-state V´= 23 V´= 24 2hv 2hv J(J+1) J(J+1)
Lay:1, Gr:1 Lay:9, Gr:10

20. D35Cl, V-state V´= 25 V´= 26 2hv 2hv J(J+1) J(J+1)
Lay:3, Gr:3 Lay:10, Gr:11

21. D35Cl, V-state V´= 27 V´= 28 2hv 2hv J(J+1) J(J+1)
Lay:5, Gr:5 Lay:6, Gr6

22. D35Cl, V-state V´= 29 2hv J(J+1)
Lay:7, Gr:7

23. D35Cl, V-state
Our
data B´ v´
Lay:11, Gr:8

24. D35Cl
V-state
DE=
E(v´+1)-
E(v´)
Our
data
v´+ 1/2
Lay:12, Gr:12

25. https://notendur.hi.is/~agust/rannsoknir/papers/jcp86-5273-87.pdf :
In terms of perturbation effects on the V state of DCl check E vibrational states:
1) : :
V´= 11
V´= 14 :
V´= 21

26. 2) https://notendur.hi.is/~agust/rannsoknir/papers/jcp105-10251-96.pdf
See table 5, page 1654:
NB: The cm-1 state is wrongly assigned as the
H(v´=0) state

27.
Should be
E state

28. Wang added
-v´= 20
-Some low J´peaks and
-Reanalysed some spectra (v´=22,24,26,29)
Changes can be seen my comparing
and
Main effects are seen in next slides:

29. Most probably this is E(v´=2)
D35Cl, V-state
V´= 22
Added two new peaks(?)
Before: after:
2hv
J(J+1)
J(J+1)
Most probably this is E(v´=2)

30. Increase of number of peaks: 8 peaks to 11 peak! V´= 24
D35Cl, V-state
Added new peaks(?)
Increase of number of peaks:
8 peaks to 11 peak!
V´= 24
2hv
Before: after:
V´= 23
J(J+1)

31. D35Cl, V-state V´= 26 Added new peaks(?) Before: after: 2hv J(J+1)

32. D35Cl, V-state V´= 29 Added new peak 2hv Before: after: J(J+1) V´= 28

33. D35Cl, V-state
Our
Data, newer; Wang
Data, older
See above B´
( )
This is E(v´=2)
Not V(v´=22)!
See below
NB: Big difference
in values v´
v´= 23 – 29 need to be
shifted down by 1
See below
sheet: “v´=20-29” Lay:11, Gr:8

34. D35Cl
V-state
DE=
E(v´)-
E(v´-1)
Our data, newer; Wang
Our
Data, older
See above
NB: v´= 23 – 29 need to be
shifted down by 1
See below which affects DE
See slides 35-36 v´
v´+ 1/2
sheet: “v´=20-29” Lay:12, Gr:12

35. D35Cl E/cm-1 Needs to be corrected! v´= 22 DE=E(v´)-E(v´-1)25
E/cm-1
Needs to be corrected! 20
v´= 22
DE=E(v´)-E(v´-1)
, Lay:18, Gr:18

36. D35Cl Wang et.al. 2016 E/cm-1 v´=2 Douglas & Greening,´79 v´=0 ( )
Guess
v´= 24
Wang et.al. 2016
E/cm-1
v´=2 21
Guess 17
Douglas & Greening,´79
v´=0 14
E 1S+
( ) 11
Estimated
Based on
E(v´=11)
from
Callaghan
et al.´87 7
Coxon et al., ´88
V 1S+
DE=E(v´)-E(v´-1)
Gr:18, Lay:18
sheet: “T0 and B´s summary”

37. https://notendur. hi. is/~agust/rannsoknir/rempi/dcl/XLS-161213
sheet: “T0 and B´s summary”

38. DCl, V state: E(v´=8-11) estimated:
sheet: “T0 and B´s summary”
DCl, V state: E(v´=8-11) estimated:
sheet: “various things”

39. Coefficient values ± one standard deviation
a = ± = intersect
b = ± =slope
DE=E(v´)-E(v´-1)
E(middle)
Gr:19, Lay:19

40. Coefficient values ± one standard deviation
a = ± = intersect
b = ± 0.14 =slope
DE=E(v´)-E(v´-1)
V´(middle)
Gr:20, Lay:20

41. D35Cl ? Wang et.al. 2016 E/cm-1 v´=2 Douglas & Greening,´79 v´=0 Guess21
Guess 17
Douglas & Greening,´79
v´=0 14
E 1S+ 11
Guess 7
Coxon et al., ´88
V 1S+ B´
Gr:21, Lay:21
sheet: “T0 and B´s summary”

42. D35Cl, V-state V´= 23 n(J) J(J+1)
Gr:23, Lay:23

43. D35Cl, V state, Tv´s vs. v´ from the literature and our data:
Blue:
green:
Black:
Pink:
Red: RJD(?)
Brown: Our data:/Wang et al.
sheet= “T0 and B´s summary”

44. D35Cl, V state (& E(v´=2)), Q lines vs
D35Cl, V state (& E(v´=2)), Q lines vs. v´ (our data) AND derived T´, B´and D´values:
v´= 2
sheet= “v´=20-28

45. DE(=E(v´)-E(v´-1)) vs. v´ for the V state
D35Cl
DE(=E(v´)-E(v´-1)) vs. v´
for the V state
v´= 28
Guess
v´= 24
Wang et.al. 2016
E/cm-1
v´=2 21
Guess 17
Douglas & Greening,´79
v´=0 14
E 1S+
( ) 11
Estimated
Based on
E(v´=11)
from
Callaghan
et al.´87 7
Coxon et al., ´88
V 1S+
DE=E(v´)-E(v´-1)
Gr:18, Lay:18
sheet: “T0 and B´s summary”

46. D35Cl B´ vs. v´ for the V state Wang et.al. 2016 E/cm-1 v´=2
Guess
v´= 24
Wang et.al. 2016
E/cm-1
v´=2 21
Guess 17
Douglas & Greening,´79
v´=0 14
E 1S+ 11
Guess 7
Coxon et al., ´88
V 1S+ B´
Gr:21, Lay:21
sheet: “T0 and B´s summary”

47. DE(=E(v´)-E(v´-1)) vs. v´ for the V state
D35Cl
DE(=E(v´)-E(v´-1)) vs. v´
for the V state
v´= 28
Guess
v´= 24
Wang et.al. 2016
E/cm-1
v´=2 21
Guess 17
Douglas & Greening,´79
v´=0 14
E 1S+
( ) 11
Estimated
Based on
E(v´=11)
from
Callaghan
et al.´87 7
Coxon et al., ´88
Deperturbed
Levels from
Perturbed levels
DE=E(v´)-E(v´-1)
Gr:18, Lay:18
sheet: “T0 and B´s summary”

48. D35Cl DE = E(v´)-E(v´-1) From perturbed levels From deperturbed
Levels in ?
V-state
(v´ + ½)
Gr:24, Lay:24
sheet: “T0 and B´s summary”

49. H35Cl
pages 312 – 320 v´ 28 19 15 10 3 v´
E(E )
DE(E )
E(V)
DE(V)
83780 3 1
2139.8 4
755.8 2
2246.9 5
729.7 6
704.5 7
681.9 8
656 9
613.9 10
83434
594.3 11
84208
774 12
539.1 13
531.3 14
393.3 15
732.9 16
527.2 17
533.4 18
502.2 19
598.1 20
520.6 21
521.2 22
499.5 23
523.3 24
515.4 25
91640
494.5 26
459.1 27
436.3 28
534.3 29
390.6 30
493 31
392.1 32
368.4 v´ 2 1
2246.9
2139.8 E V
; Lay0;Gr0

50.
sheet= “v´=20-28

51. DE(=E(v´)-E(v´-1)) vs. v´ for the V state
D35Cl
DE(=E(v´)-E(v´-1)) vs. v´
for the V state
v´= 28
Guess
v´= 24
Wang et.al. 2016
E/cm-1
v´=2 21
Guess 17
Douglas & Greening,´79
v´=0 14
E 1S+
( ) 11
Estimated
Based on
E(v´=11)
from
Callaghan
et al.´87 7
Coxon et al., ´88
V 1S+
DE=E(v´)-E(v´-1)
Gr:18, Lay:18
sheet: “T0 and B´s summary”

52. D35Cl B´ vs. v´ for the V state Wang et.al. 2016 E/cm-1 v´=2
Guess
v´= 24
Wang et.al. 2016
E/cm-1
v´=2 21
Guess 17
Douglas & Greening,´79
v´=0 14
E 1S+ 11
Guess 7
Coxon et al., ´88
V 1S+ B´
Gr:21, Lay:21
sheet: “T0 and B´s summary”

53. n0 and B´ both increase as J0 increases (J0 =0  3) Most likely
V(v´=26(a))
J0= 0
J0 = 1
J0 = 2
J0 = 3
Ki´s
DKi´s
88565
1.25
0.169
0.004
413
Ki´s
DKi´s
88577
2.52
0.23
401
Ki´s
DKi´s
88587
4.06
0.262
391
Ki´s
DKi´s
88595
5.56
0.263
383
Very big B´
n0 and B´ both increase as J0 increases (J0 =0  3)
Most likely
Completely unrealistic!
sheet= “v´=20-28

54. v´= 26; J0 = 1 J0 = 2 Wang et.al. 2017 Wang et.al. 2017 E/cm-1 E/cm-1
Guess
Guess
Wang et.al.
2017
v´= 24
v´= 24
Wang et.al. 2017
E/cm-1
E/cm-1
v´=2
v´=2 21 21
Guess
Guess 17 17
Douglas &
Greening,´79
Douglas & Greening,´79
v´=0
v´=0 14 14
E 1S+
E 1S+
( )
( ) 11 11
Estimated
Estimated
Based on
E(v´=11)
from
Callaghan
et al.´87
Based on
E(v´=11)
from
Callaghan
et al.´87 7 7
Coxon et al., ´88
Coxon et al., ´88
V 1S+
V 1S+
DE=E(v´)-E(v´-1)
DE=E(v´)-E(v´-1)
Gr:18, Lay:18
Gr:18, Lay:18

55. v´= 26; J0 = 1 J0 = 2 For new values based on D37Cl from Arnar
Guess
Guess
Wang et.al.
2017
v´= 24
v´= 24
Wang et.al. 2017
E/cm-1
E/cm-1
v´=2
v´=2 21 21
Guess
Guess 17 17
Douglas &
Greening,´79
Douglas & Greening,´79
v´=0
v´=0 14 14
E 1S+
E 1S+
( )
( ) 11 11
Estimated
Estimated
Based on
E(v´=11)
from
Callaghan
et al.´87
Based on
E(v´=11)
from
Callaghan
et al.´87 7 7
Coxon et al., ´88
Coxon et al., ´88
V 1S+
V 1S+
DE=E(v´)-E(v´-1)
DE=E(v´)-E(v´-1)
Gr:18, Lay:18
Gr:18, Lay:18

56. v´= 26; J0 = 1 J0 = 2 Wang et.al. 2017 Wang et.al. 2017 E/cm-1 E/cm-1
Guess
Wang et.al.
2017
Guess
v´= 24
v´= 24
Wang et.al. 2017
E/cm-1
E/cm-1
v´=2
v´=2 21 21
Guess
Guess 17
Douglas &
Greening,´79 17
Douglas &
Greening,´79
v´=0
v´=0 14 14
E 1S+
E 1S+ 11 11
Guess
Guess 7 7
Coxon et al., ´88
Coxon et al., ´88
V 1S+
V 1S+ B´ B´
Gr:21, Lay:21
Gr:21, Lay:21

57. v´= 26; J0 = 1 J0 = 2 For new values based on D37Cl from Arnar
Guess
Wang et.al.
2017
Guess
v´= 24
v´= 24
Wang et.al. 2017
E/cm-1
E/cm-1
v´=2
v´=2 21 21
Guess
Guess 17
Douglas &
Greening,´79 17
Douglas &
Greening,´79
v´=0
v´=0 14 14
E 1S+
E 1S+ 11 11
Guess
Guess 7 7
Coxon et al., ´88
Coxon et al., ´88
V 1S+
V 1S+ B´ B´
Gr:21, Lay:21
Gr:21, Lay:21

58. Blue values are „new“, i.e. added 170411
Now new lines are needed from Arnar
sheet= “v´=20-28

59. Blue values are „new“, i.e. added 170411
New values from Arnar ( , „V(23) m.v. D35Cl” ,
have been added:
Blue values are „new“, i.e. added
See slides below (no ):
sheet= “v´=20-28

60. v´= 26; J0 = 1 J0 = 2 For new values based on D37Cl from Arnar
Guess
Guess
Wang et.al.
2017
v´= 24
v´= 24
Wang et.al. 2017
E/cm-1
E/cm-1
v´=2
v´=2 21 21
Guess
Guess 17 17
Douglas &
Greening,´79
Douglas & Greening,´79
v´=0
v´=0 14 14
E 1S+
E 1S+
( )
( ) 11 11
Estimated
Estimated
Based on
E(v´=11)
from
Callaghan
et al.´87
Based on
E(v´=11)
from
Callaghan
et al.´87 7 7
Coxon et al., ´88
Coxon et al., ´88
V 1S+
V 1S+
DE=E(v´)-E(v´-1)
DE=E(v´)-E(v´-1)
Gr:18, Lay:18
Gr:18, Lay:18

61. v´= 26; J0 = 1 J0 = 2 For new values based on D37Cl from Arnar ?
Guess
Wang et.al.
2017
Guess
v´= 24
v´= 24
Wang et.al. 2017
E/cm-1
E/cm-1
v´=2
v´=2 21 21
Guess
Guess 17
Douglas &
Greening,´79 17
Douglas &
Greening,´79
v´=0
v´=0 14 14
E 1S+
E 1S+ 11 11
Guess
Guess 7 7
Coxon et al., ´88
Coxon et al., ´88
V 1S+
V 1S+ B´ B´
Gr:21, Lay:21
Gr:21, Lay:21

62. ? ? DEJ,J-1 v´= 17 v´= 18 J The high levels according D35Cl
to VHW are STRANGE!
D35Cl ?
From Wang
DEJ,J-1
V(v´=17 & 18) ?
The high levels according to
VHW are STRANGE!
Possibly some negative curvature
Which could be due to the interaction
Between E(v´=1) and V(v´=17)
From Dagdigian
v´= 17
v´= 18
Shows positive curvature
Which could be due to the interaction between
E(v´=1) and V(v´=18) J
Lay: 24, Gr: 24
sheet= “v´=17,18”

63. DEJ,J-1 DEJ,J-1 J J DCl, V(v´) states DEJ,J-1 vs. J v´= 22 Positive
sheet= “DE vs J”
v´= 22
Positive
curvature
because of
effect from
E(v´=2)
v´= 20 v´= 21
v´= 22
v´= 23
v´= 24
v´= 24 v´= 25 v´= 26 (J0 = 2)
v´= 27
v´= 28
? See also next slide J J
Lay: 25, Gr: 25
Lay: 26, Gr: 26

64. DEJ,J-1 J DCl, V(v´=26) states DEJ,J-1 vs. J (J0 = 2) v´= 26 (J0 = 2)
Could this simply be
35Cl+ signal from H35Cl!
(J0 = 1)
(J0 = 0) J
Lay: 27, Gr: 27

65. HCl
B´= 7.5 => HCl!
sheet= “v´=20-28

66. DEJ,J-1
Also: J
Lay: 28, Gr: 28
sheet= “DE vs J”

67. V´ ? ?
sheet= “T0 and B´s summary”

68. E/cm-1 V HCl E DCl V ( ) E V guessed DE=E(v´)-E(v´-1)/ cm-1 ? ?22 28 ? V 3 24 2 18 2 21 1 14 ? 17 1 14
0 = v´ 10 E
( ) 11
V guessed
Questionable: Based on
E(v´=11)
from
Callaghan
et al.´87 3
V´= 0
DE=E(v´)-E(v´-1)/
cm-1
Gr:18, Lay:24

69. E/cm-1 HCl E DCl E V guessed V V B´ / cm-1 guessed ? ? v´= 3 22 28 3 224 18 2 21 1 14 1 ? 17
v´= 0 ´ 14 10 11
V guessed
guessed V V 3
v´= 0
B´ / cm-1
Gr:21, Lay:25

70. HCl DCl E/cm-1 V E V guessed E DE=E(v´)-E(v´-1)/ cm-1 ? ? 3 22 28 2 318 24 2 21 1 14 1 ? 17 14 10 11 V
guessed E 3
v´= 0
DE=E(v´)-E(v´-1)/
cm-1
Gr:18, Lay:24

71. HCl V E/cm-1 DCl E V E B´ / cm-1 guessed ? ? v´= 3 22 28 2 3 18 24 221 1 14 ? 1 17
v´= 0 14 10 11
guessed 3
v´= 0
B´ / cm-1
Gr:21, Lay:25