1. CH3Br, one-color exp.: CHn+, iBr+ and CiBr+ ions vs CH3Br(Ry) states:
Content: pages:
Images and KERs: KERs for Ry(66019) and Ry(72977)…………………………………………………………………. 2-3 Comments concerning CH3+ signal for Ry(66019)……………………………………… ….. 4
Comments concerning Br+ signal for Ry(66019)…………………………………………….. 5 KERS vs. Ions and 2hv…………………………………………………………………………………….. 6 CH3+; KERs and images ………………………………………………………………………………… CH3+ interpretation ………………….…………………………………………………………………… 18-19
CH2+; KERs and images …………………………………………………………………………………
CH+; KERs ……………………………………………………………………………………………………… 25-26
79Br + ; KERs and images ..………………………………………………………………………………
C79Br + ;KERs …………………………………………………………………………
Comparison of xx and zz KER spectra……………………………………………………………… 34-38
Energetics with respect to possible CH3+ and CH2+ formation………………………… 39-45
Ry(78370): images and KERs, CHn+, 79Br+, C79Br+……………………………………… Comparison of C79Br+ and C81Br+(CH279Br+) signals for
Ry(67275; )……………………………………………………………………………………….. 50
1hv vs 2hvr spectra contributions……………………………………………………………………… 51,64 spectra vs thresholds………………………………………………………………………………………… 52-57
Comparison of using different „pix -> eV factors „(2.72x10-5 vs. 2.98x10-5…… 56-57
Vibr. Structure vs. 3hv and 1hv excitations……………………………………………………… 58-59
CH3Br+ -> CH3+ + Br/Br* (?)…………………………………………………………………………… 62-63
Vibrational analysis of the CH3**(3p2A2) Rydberg state…………………………………
Angular distributions: CH3+…………………………………….……………………………………………………………………
CH2+(under construction)………………………………………….………………………………………
CH+………………………………….………………………………………….………………………………………
Br+……………………………………………………………………………………………………………………
CBr+…………………………………………………………………………………………………………………… comparison of CH3+, CH2+ (and CH+, C+) signals…………………………………………………
Updated:

2. KERs(xx): Ry(2hv/cm-1): CH3+ CH2+ CH+ C+ 72977(from 7.9.16)
To top
Ry(2hv/cm-1):
72977(from )
66019 (from )
CH3+
CH2+
CH+ C+ eV
Gr:9, Lay:0
date:

3. KERs(xx): Ry(2hv/cm-1): 72977(from 7.9.16) 79Br+ C79Br+
To top eV
0.111 eV
Ry(2hv/cm-1):
72977(from )
66019 (from )
79Br+
C79Br+
Calc. energy for CH3 + Br (<= Arnar; ): 0.179eV
Calc. energy for CH3 + Br*(<= Arnar; ): eV
0.170 eV eV
81Br+
C79Br+ eV
Gr:10, Lay: 1
date:

4. CH3+:
Five criterias have been looked at concerning possible explanations of the structure observed
For CH3+, Ry(66019) (slide 2; red curve, bottom) (see AK´s notes from ):
1hv excitation of CH3Br to repulsive valence states ruled out, since signal must involve excitation followed by dissociation to form CH3/CH3 (v´´) + Br/Br* via higher enenergy CH3Br Rydberg state followed by multiphoton ionization of CH3/CH3(v´´) (i.e the Ry(66019 state))
2hv resonance excitation of CH3Br to the Ry(66019) state ruled out, for energetic reasons: Would involve followed by dissociation to form CH3/CH3 (v´´) + Br/Br* much higher KER´s than what is observed. followed by multiphoton ionization CH3/CH3 (v´´)
3hv excitation of CH3Br ruled out, for energetic reasons: Would involve followed by dissociation to form CH3+/CH3+ (v+) + Br- higher KER´s than what is observed. followed by multiphoton ionization CH3/CH3 (v´´)
3hv excitation of CH3Br followed by dissociation to form CH3**/CH3 (v´)** + Br Possible energetically but no detaild (CH3**/CH3 (v´)** are neutral excited states) conclusion followed by multiphoton ionization of CH3**/CH3 (v´)**
4hv excitation of CH3Br to form CH3Br+ ruled out, for energetic reasons: Would involve followed by dissociation to form CH3+/CH3+ (v+) +Br/Br* higher KER´s than what is observed.
To top
Due to (2), (3) and (5) above: Check to see if CH3+ signals are observe for higher KERS
190908: Measured Ry(66019) for repeller voltage = 5kV (instead of 3kV):
No signals obserd for higher KERs
date:

5. 1. Most likely candidate for the Br+ formation is the channel:
To top
Br+:
1. Most likely candidate for the Br+ formation is the channel:
1hv excitation. followed by dissociation to form CH3 + Br/Br* followed by multiphoton excitation of Br/Br* (see slide 3) 2. Might be that the ratio of the two channels (with respect to Br and Br* formation) vary by going from Ry(66019) to Ry(72977) (see slide 3)
Will be interesting to see how/whether the Br+ peak shifts „regularely“ as we go stepwise
From Ry(66019) to Ry(72977)
date:

6. KERs(xx): CH3+ CH2+ CH+ C+ CH3+ +Br- eV Ry(2hv/cm-1): 72977(7.9.16)
To top
CH3+
CH2+
CH+ C+
Ry(2hv/cm-1):
72977(7.9.16)
66503(8.9.16)
66019 (6.9.16)
CH3+
+Br- eV
Gr:9, Lay:0
date created:

7. To top
CH3+

8. KERs (xx): CH3+ eV Ry(2hv/cm-1): 78370(12.9.16) 77165(15.9.16)
To top
CH3+
Ry(2hv/cm-1):
78370( )
77165( )
75905( )
74249( )
72977(7.9.16)
68684( )
67275( ))
66503(8.9.16)
66019 (6.9.16)
CH3+
+Br- eV
Gr:11, Lay:2
date created:

9. KERs (xx): CH3+ eV Ry(2hv/cm-1): 78370(12.9.16) 77165(15.9.16)
To top
CH3+
Ry(2hv/cm-1):
78370( )
77165( )
75905( ) )
72973(7.9.16)
68684( )
67275( ))
66503(8.9.16)
66019 (6.9.16)
CH3+
+Br- eV
Gr:11, Lay:2
date created:

10. KERs (xx): CH3+ eV Ry(2hv/cm-1): 79610 (16.09.16) 78370(12.9.16)
To top
CH3+
Ry(2hv/cm-1):
79610 ( )
78370( )
77165( )
75905( ) )
72973(7.9.16)
68684( )
67275( ))
66503(8.9.16)
66019 (6.9.16)
CH3+
+Br- eV
Gr:11, Lay:2
date created:

11. CH3+ REMPI specttra (1/2)6p w = 2 0 5d (3/2)6d w = 2 0 To top
REMPI spectra pxp

12. KERs (xx): CH3+ n =6; n2 n=7; w = 0; (3/2)np n = 6 w = 2 0; (1/2)np
To top
CH3+
Ry(2hv/cm-1):
77165 ( )
( )
78370( )
( )
79610 ( )
n =6; n2
n=7; w = 0; (3/2)np
CH3+
+Br-
n = 6 w = ; (1/2)np
n = 5; w = ; (3/2)nd eV
Gr:27Lay:16
date created:

13. KERs (xx): CH3+ n =6; n2 n=7; w = 0; (3/2)np n = 6 w = 2 0; (1/2)np
To top
CH3+
Ry(2hv/cm-1):
77165 ( )
( )
78370( )
( )
79610 ( )
n =6; n2
n=7; w = 0; (3/2)np
CH3+
+Br-
n = 6 w = ; (1/2)np
n = 5; w = ; (3/2)nd eV
Gr:27Lay:16
date created:

14. Images (xx): CH3+ CH3+ +Br- Ry(2hv/cm-1): 67275(13.9.16))
To top
Ry(2hv/cm-1):
67275( ))
66503(8.9.16)
66019 (6.9.16)
CH3+
+Br-
Gr:11, Lay:2
date created:

15. KERs (xx): CH3+ CH3+ +Br- Ry(2hv/cm-1): 74249(15.9.16) 72973(7.9.16)
To top
Ry(2hv/cm-1):
74249( )
72973(7.9.16)
68684( )
CH3+
+Br-
Gr:11, Lay:2
date created:

16. KERs (xx): CH3+ CH3+ +Br- Ry(2hv/cm-1): 78370(12.9.16) 77165(15.9.16)
To top
Ry(2hv/cm-1):
78370( )
77165( )
75905( )
Gr:11, Lay:2
date created:

17. KERs (xx): CH3+ eV Ry(2hv/cm-1): 66019 (6.9.16; MOPO)
66019 ( ; Dye laser)
To top
CH3+ eV
Gr:44, Lay:31

18. Clear shift of peaks as 66019 -> 66503
To top
CH3+:
Clear shift of peaks as > 66503
More peaks appear as > 66503
Peak structure looks like vibrational structure
Possible interpretation:
Molecular
excitation
Dissoci-
ation
Fragment
ionization
CH Br/Br*
1hvi
Intensity
CH3**(v´+n) + Br/Br* :
CH3**(v´) Br/Br*
1hvpd
CH3Br** (Ry)
KER
Vibrational ladder for
a particular
vibrational mode
(for example OPLA
vibration)
2hvr
CH3Br

19. Possible explanation for rings observed in the CH3+ spectra:
To top
CH3+ + Br**(i)
CH3Br#
(5) :
CH3* + Br**(i) :
(4)
(3)
(2)
(1)
CH3* + Br**(1)
CH3Br**
i.e.
(2r+2+1i)REMPI
5hv
CH3Br

20. To top
CH2+

21. KERs (xx): CH2+ Ry(2hv/cm-1): CH3+ + Br- 79610(16.9.16) 78370(12.9.16)
To top
CH2+
Ry(2hv/cm-1):
79610( )
78370( )
77165( )
75905( ) 74249( )
72973(7.9.16)
68684( )
67275( ))
66503(8.9.16)
66019 (6.9.16)
CH3+
+ Br-
Gr:12, Lay:3
date created:

22. Images (xx): CH2+ CH3+ + Br- Ry(2hv/cm-1): 67275(13.9.16))
To top
Ry(2hv/cm-1):
67275( ))
66503(8.9.16)
66019 (6.9.16)
CH3+
+ Br-
Gr:12, Lay:3
date created:

23. KERs (xx): CH2+ CH3+ + Br- Ry(2hv/cm-1): 75905(14.9.16 72973(7.9.16)
To top
Ry(2hv/cm-1):
75905(
72973(7.9.16)
68684( )
CH3+
+ Br-
Gr:12, Lay:3
date created:

24. KERs (xx): CH2+ CH3+ + Br- Ry(2hv/cm-1): 78370(12.9.16) To top
Gr:12, Lay:3
date created:

25. To top
CH+

26. KERs (xx): CH+ Ry(2hv/cm-1): 78370(12.9.16)
To top
CH+
Ry(2hv/cm-1):
78370( )
75905( ) 72977(7.9.16)
68684( )
67273 ( )
66019 (6.9.16)
CH3+
+ Br-
Gr:23, Lay:12
date created:

27. To top
79Br+

28. KERs (xx): 79Br+ Ry(2hv/cm-1): CH3+ + Br- 79610(16.9.16)
To top
79Br+
Ry(2hv/cm-1):
79610( )
78370( )
77165( )
75905( )
72977(7.9.16)
68684( ) ( )
66019 (6.9.16)
CH3+
+ Br-
Gr:24, Lay:13
date created:

29. KERs (xx): 79Br+ Ry(2hv/cm-1): 68684(14.9.16) 67273 (13.9.16)
To top
79Br+
Ry(2hv/cm-1):
68684( ) ( )
66019 (6.9.16)
CH3+
+ Br-
Gr:24, Lay:13
date created:

30. KERs (xx): 79Br+ Ry(2hv/cm-1): 78370(12.9.16) 75905(14.9.16)
To top
79Br+
Ry(2hv/cm-1):
78370( )
75905( )
72977(7.9.16)
CH3+
+ Br-
Gr:24, Lay:13
date created:

31. KERs (xx): 79Br+ Ry(2hv/cm-1): 79610(16.9.16) CH3+ + Br- To top
Gr:24, Lay:13

32. To top
C79Br+

33. KERs (xx): C79Br+ Ry(2hv/cm-1): 78370(12.9.16) 72977(7.9.16)
To top
C79Br+
Ry(2hv/cm-1):
78370( )
72977(7.9.16)
68684( )
67273 ( )
66019 (6.9.16)
CH3+
+ Br-
Gr:25, Lay:14
date created:

34. To top
X vs Z data:

35. KERs (xx) & (zz): CH3+ eV Ry(2hv/cm-1): 66503(8.9.16) To top
Gr:13, Lay:4
date created:

36. KERs (xx) & (zz): CH3+ eV Ry(2hv/cm-1): 66019(6.9.16) To top
Gr:13, Lay:4
date created:

37. KERs (xx) & (zz): CH3+ eV Ry(2hv/cm-1): 77165(15.9.16) To top
Gr:28, Lay:17
date created:

38. KERs (xx) & (zz): CH3+ eV Ry(2hv/cm-1): 79610(16.9.16) To top
Gr:29, Lay:18
date created:

39. To top
Energetics

40. Energetics with respect to possible CH3+ formation:
To top
Study range cm-1
Energetics with respect to possible CH3+ formation:
33009
99029
66019
33009
r/A
Gr:0; Lay:0

41. Energetics with respect to possible CH3+ formation:
To top
Study range cm-1
Energetics with respect to possible CH3+ formation:
2hn
1hn
r/A
„various things“
Gr:0; Lay:0

42. NB: 2hv excitations 66019 – 68684 cm-1 < CH3**(3s 2A1) + Br/Br*
3hv excitations – cm-1 < CH3+ + Br/Br*
3hv excitations – cm-1 > CH3+ + Br/Br*

43. Energetics with respect to possible CH3+ formation
To top
Study range cm-1
Energetics with respect to possible CH3+ formation
And CH3 ionizations:
3hni
1hn
r/A
„various things“
Gr:0; Lay:0

44. NB:
The cm-1 2hv excitation corresponds to switching from the need of three-photons
to only need of two-photons to ionize CH3(X, 0000), which might explain the
observed enhancements in some of the „1hv“ CH3+ signals (?)

45. To top refs in Theos, 2014 paper l/nm cm-1 year ref: Theo,2014 193
2014 2
215 to 251
39840 to 46512
1998 3
193,222
45045, 51813
1985 4
205
48780
1992 5
213, ca.230
43478, 46948
2007 6
216
46296
2009 7
240 to 280
35714 to 41667
2000
Gr:0; Lay:0
„1hv phd“

46. Energetics with respect to possible CH2+ formation:
To top
Study range cm-1
Energetics with respect to possible CH2+ formation:
66019
33009
33009
99029
66019
33009
CH3**+Br
r/A
Gr:0; Lay:0

47. To top
Images vs.
KERs:

48. Ry(78370); 255.233 nm; Date: 160912 CH3+ CH2+ CH+ KERs: eV To top
Gr:17,Lay: Gr:18,Lay:7, Gr:19,Lay:8

49. Hint of a „shoulder“ from the „blob“
Ry(78370); nm; Date:
To top
CH3+
CH2+
Hint of a „shoulder“ from the „blob“ eV
Gr:17,Lay:9

50. Ry(78370); 255.233 nm; Date: 160912 79Br+ C79Br+ KERs: eV To top
Gr:20,Lay:1; Gr:21, Lay:10

51. Comparison for C79Br+ and C81Br+(CH279Br+) signals for
Ry(67275; ):
To top
Virtually identical eV
Gr:26, Lay:15
date created:

52. 2hvr: signals following
Bands according to
(T. Ridley et al. CH3Br paper, 2008)
To top
66019
75686
75905
n = 5
[3/2]np;w 6 7 2
w = n3 n2 n1 n3 n2 5
[1/2]np;w
78370 6
79610 2 2 n3 n2
68461
68684
78225
72977
80640
80758 4
[3/2]nd;w 6 2 2 2 n3 n2 n1 4
[1/2]nd;w 5
72655 2
75418
78401
2hvr: signals following
two-photon
resonance excitation n3 n2
78193
80674
80881
1hv: Signals following
one-photon excitation
77515 cm-1
REMPI spectra pxp; Gr:0; Lay:0

53. Relative intensity nhv excitations n = 1,2,3,… 3Dhn Threshold (2)
To top
Relative intensity
nhv excitations
n = 1,2,3,…
3Dhn
Threshold (2)
Threshold (1)
KER spectra

54. 3hv excitations 3Dhn/eV Thresholds 79610 (16.09.16) 78370(12.9.16)
77165( )
75905( ) )
Ry(2hv/cm-1) KERs:
72973(7.9.16)
68684( )
67275( ))
66503(8.9.16)
66019 (6.9.16)
To top
3hv excitations
CH3(4f2E)+Br*
CH3(4p2A2)+Br*
CH3(4f2E)+Br
CH3(4p2A2)+Br
CH3(3d2A1)+Br*
3Dhn/eV
CH3(3d2E)+Br*
CH3(3d2A1)+Br
CH3(3d2E)+Br
CH3(3p2A2)+Br*
CH3(3p2A2)+Br
Thresholds
CH3;one-color 
Gr:61, Lay:45

55. 1hv excitations Dhn/eV Thresholds Hot bands, i.e. due to
79610 ( )
78370( )
77165( )
75905( ) )
Ry(2hv/cm-1) KERs:
72973(7.9.16)
68684( )
67275( ))
66503(8.9.16)
66019 (6.9.16)
To top
1hv excitations
CH3(0010)+Br*(0.8722)
CH3(1000)+Br*(0.8885)
CH3(0001)+Br*(1.0555)
CH3(0100)+Br*(1.1384)
Dhn/eV
(1.2562)CH3(0010)+Br
CH3(0000)+Br* (1.2016)
(1.2725)CH3(1000)+Br
(1.4394)CH3(0001)+Br
CH3(0100)+Br(1.5224)
CH3(0000)+Br(1.5856)
Thresholds
Hot bands, i.e. due to
Vibrationall „hot“ CH3Br#
CH3;one-color 
Gr:62, Lay:47

56. Effect of using different scaling factors (f) for transfering
To top
Effect of using different
scaling factors (f) for transfering
pixels to eV:
See slide above
3hv excitations #
eV* eV
Gr:61, / * Gr:63
# f = 2.72 x 10-5; *f= 2.98x10-5

57. Effect of using different
To top
Effect of using different
scaling factors (f) for transfering pixels to eV:
CH3(0000)+Br*(1.2016)
CH3(0001)+Br*(1.0555)
CH3(0100)+Br(1.5224)
CH3(0010)+Br*(0.8722)
CH3(1000)+Br*(0.8885)
See slide above
1hv excitations # eV
eV*
Gr:62, / * Gr:64
# f = 2.72 x 10-5; *f= 2.98x10-5

58. 3hv excitations eV* 3Dhn To top 68684(14.9.16) 67275(13.9.16))
66503(8.9.16)
66019 (6.9.16)
3hv excitations
eV*
3Dhn
Gr:63
*f= 2.98x10-5

59. 1hv excitations eV* To top 68684(14.9.16) 67275(13.9.16))
66503(8.9.16)
66019 (6.9.16)
1hv excitations
eV*
Gr:63
*f= 2.98x10-5

60. Judging from slides 58 and 59:
To top
NB:
Judging from slides 58 and 59:
Although not perfect fit of vibrational peaks it seems to be slightly better for
3hv-shifts (hence CH3**(3p 2A2) + Br/Br* formation))
Rather than for
1hv -shift (hence CH3Br+ -> CH3+ + Br* formation
-suggesting that the former mechanism holds.

61. excitations 1hv DE/eV Thresholds 79610 (16.09.16) 78370(12.9.16)
77165( )
75905( )
Ry(2hv/cm-1) KERs:
To top
excitations
1hv
CH3(0010)+Br*(0.8722)
CH3(1000)+Br*(0.8885)
CH3(0001)+Br*(1.0555)
CH3(0100)+Br*(1.1384)
b2 =
CH3(0000)+Br*(1.2016)
CH3(0010)+Br (1.2562)
b2 =
b2 =
CH3(1000)+Br(1.2725)
b2 =
CH3(0001)+Br(1.4394)
b2 =
CH3(0100)+Br(1.5224)
CH3(0000)+Br(1.5856)
b2 =
DE/eV
b2 =
Thresholds
b2 =
CH3;one-color 
Gr:62, Lay:47

62. excitations 1hv DE/eV Thresholds corresponding to tranitions from
Ry(2hv/cm-1) KERs:
77165 ( )
( )
78370( )
( )
79610 ( )
To top
excitations
1hv
v5(def.) = 1
DE/eV
v3(def.) = 1
v1(CH-str.) = 1
vi = 0
v5(def.) = 1
CH3+(v1,..v6) + Br*
v3(def.) = 1
v1(CH-str.) = 1
vi = 0
CH3+(v1,..v6) + Br
Thresholds corresponding to tranitions from
CH3Br+(0,0,0,0..) (see next slide)
CH3;one-color 
Gr:61, Lay:45

63. 1hv # Superexcited state Autoionization KER(Br*) KER(Br)
CH3+(v1,v2,..) + Br*
CH3+(v1,v2,...) + Br
CH3Br+
(0,0…)
Superexcited state
Autoionization

64. 2hvr: signals following
Ry(2hv/cm-1) KERs:
To top
Example of a
1hv and 1hvr
signal contributions in a
CH3 KER spectrum:
77165 ( )
1hv: Signals following
one-photon excitation
2hvr: signals following
two-photon
resonance excitation eV
Gr:62, Lay:46

65. Vibrational analysis of the CH3**(3p 2A2) Rydberg state:
To top
Vibrational analysis of the CH3**(3p 2A2) Rydberg state:
Vibrational energies from NIST for CH3*2: 3p 2A2 state
Slide 4*:
Vibrational energy difference estimated around ~1000 cm-1 eV
Estimation of peak v=n for OPLA
CH3*2 => v=10
CH3*3 => v=4
CH3*4 => v=4
*….Dropbox/REMPI/From Arnar/CH3Br/Focus on first 4 peaks _regarding vibrational ladder.pptx ;

66. D0 stands for CH3Br -> CH3 + Br
66503 cm-1
Slide 5*:
D0 stands for CH3Br -> CH3 + Br
*….Dropbox/REMPI/From Arnar/CH3Br/Focus on first 4 peaks _regarding vibrational ladder.pptx ;

67. D0 stands for CH3Br -> CH3 + Br
66503 cm-1
Slide 5*:
D0 stands for CH3Br -> CH3 + Br eV
*….Dropbox/REMPI/From Arnar/CH3Br/Focus on first 4 peaks _regarding vibrational ladder.pptx ;

68. Slide 9*:
*….Dropbox/REMPI/From Arnar/CH3Br/Focus on first 4 peaks _regarding vibrational ladder.pptx ;

69. Slide 10*:
*….Dropbox/REMPI/From Arnar/CH3Br/Focus on first 4 peaks _regarding vibrational ladder.pptx ;

70. To top
Angular
distributions:
X files

71. To top
CH3+:

72. CH3+ pix q Ry(2hv/cm-1): 66019(6.9.16) To top b2 = 1.3838 b2 = 1.2627
Gr:32, Lay:19
Gr:24, Lay:10
angul.d. 

73. CH3+ pix q Ry(2hv/cm-1): 66503(8.9.16) To top b2 = 0.88204
Gr:33, Lay:20
Gr:24, Lay:11
angul.d. 

74. CH3+ pix q Ry(2hv/cm-1): 67275(13.9.16) To top b2 = 1.1489 b2 = 1.1593
Gr:34, Lay:21
Gr:22, Lay:12
angul.d. 

75. CH3+ pix q Ry(2hv/cm-1): 68684(14.9.16) To top b2 = 0.81842
Gr:35, Lay:22
Gr:26, Lay:13
angul.d. 

76. CH3+ pix q Ry(2hv/cm-1): 72977(7.9.16) To top b2 = 2.0226
Gr:38, Lay:25
Gr:28, Lay:16
angul.d. 

77. CH3+ pix q Ry(2hv/cm-1): 74249(15.9.16) To top b2 = 1.3393
Gr:37, Lay:24
Gr:27, Lay:15
angul.d. 

78. CH3+ pix q Ry(2hv/cm-1): 75905(14.9.16) To top b2 = -0.049622
Gr:36, Lay:23
Gr:25, Lay:14
angul.d. 

79. CH3+ X Z eV q Ry(2hv/cm-1): 77165(15.9.16) To top b2 = 1.0978
Gr:20, Lay:8

80. CH3+ X Z eV q Ry(2hv/cm-1): 79610(16.9.16) To top b2 = 1.4741
Gr:19, Lay:7

81. CH3+
Gr:11, Lay:2
To top
Gr:21, Lay:9

82. CH3+
To top b2
Gr:47

83. To top
CH2+:
Under construction

84. CH2+ pix q Ry(2hv/cm-1): 66019(6.9.16) To top b2 = 2.0185 b2 = 1.7032
Gr:40, Lay:27
Gr:50, Lay:37
angul.d. 

85. CH2+ pix q Ry(2hv/cm-1): 66503(8.9.16) To top b2 = 1.0753 b2 = 1.0054
Gr:41, Lay:28
Gr:51, Lay:38
angul.d. 

86. CH2+ pix q Ry(2hv/cm-1): 67275(13.9.16) To top b2 = 1.3756 b2 = 1.2916
1.1152
b2 = 1.059
b2 =
pix q
Gr:42, Lay:29
Gr:52, Lay:39
angul.d. 

87. CH2+ pix q Ry(2hv/cm-1): 68684(14.9.16) To top b2 = 1.7498 b2 = 1.4938
1.3614
b2 =
pix
b2 = q
Gr:43, Lay:30
Gr:53, Lay:40
angul.d. 

88. CH3+
To top b2
Gr:58

89. CH2+
To top
b2 increases with KER, i.e. Parallel character increases with KER -for all the Ry resonances (66019 – cm-1)

90. To top
CH+:

91. CH+ pix Ry(2hv/cm-1): 66019 (6.9.16) To top b2 = 2.1339
Gr:51, Lay:37
Gr:55, Lay:42
angul.d. 

92. CH+ pix Ry(2hv/cm-1): 67275 (13.9.16) To top b2 = 1.2698 b2 = 1.3594
Gr:52, Lay:38
Gr:55, Lay:42
angul.d. 

93. CH+ pix Ry(2hv/cm-1): 68684(14.9.16) To top b2 = 1.5498
Gr:53, Lay:39
Gr:55, Lay:42
angul.d. 

94. CH+ pix Ry(2hv/cm-1): 72977(7.9.16) Ry(2hv/cm-1): 72977(7.9.16) To top
b2 =
Ry(2hv/cm-1):
72977(7.9.16)
pix
Gr:54, Lay:40
Gr:55, Lay:42
angul.d. 

95. CH+ pix Ry(2hv/cm-1): 75905(14.9.16) To top b2 = 1.1067
Gr:55, Lay:41
Gr:55, Lay:42
angul.d. 

96. CH+ pix Ry(2hv/cm-1): 78370(12.9.16) To top b2 = 0.9554
Gr:56, Lay:42
Gr:55, Lay:42
angul.d. 

97. CH+
To top b2
Gr:57

98. To top
Br+:

99. Br+ pix q Ry(2hv/cm-1): 66019 (6.9.16) To top b2 = 2.2123
Gr:38, Lay:26
angul.d. 

100. Br+ pix q Ry(2hv/cm-1): 67273 (13.9.16) To top b2 = 1.553
Gr:37, Lay:25
angul.d. 

101. Br+ pix q Ry(2hv/cm-1): 68684(14.9.16) To top b2 = 1.5328
Gr:36, Lay:24
angul.d. 

102. Br+ pix q Ry(2hv/cm-1): 72977(7.9.16) Ry(2hv/cm-1): 72977(7.9.16)
To top
Br+
Ry(2hv/cm-1):
72977(7.9.16)
b2 =
Ry(2hv/cm-1):
72977(7.9.16)
pix q
Gr:29, Lay:17
angul.d. 

103. Br+ pix q Ry(2hv/cm-1): 75905(14.9.16) To top b2 = 1.1844
Gr:39, Lay:27
angul.d. 

104. Br+ pix q Ry(2hv/cm-1): 77165(15.9.16) To top b2 = 1.1202 b2 =0.65639
Gr:35, Lay:23
angul.d. 

105. Br+ pix q Ry(2hv/cm-1): 78370(12.9.16) To top b2 = 1.2279 b2 =1.0963
Gr:34, Lay:22
angul.d. 

106. Br+ pix q Ry(2hv/cm-1): 79610(16.9.16) To top b2 =1.28 b2 =1.0372
Gr:33, Lay:21
angul.d. 

107. Br+ Br+ Low KER broad peak b2 To top
Gr:58

108. To top
C79Br+

109. C79Br+ pix Ry(2hv/cm-1): 66019 (6.9.16) To top b2 =0.59096
Gr:45, Lay:32
Gr:54, Lay:41
angul.d. 

110. C79Br+ pix Ry(2hv/cm-1): 67273 (13.9.16) To top b2 =0.09929
Gr:46, Lay:33
Gr:54, Lay:41
angul.d. 

111. C79Br+ pix Ry(2hv/cm-1): 68684(14.9.16) To top b2 =0.18756
Gr:47, Lay:34
Gr:54, Lay:41
angul.d. 

112. C79Br+ pix Ry(2hv/cm-1): 72977(7.9.16) Ry(2hv/cm-1): 72977(7.9.16)
To top
Ry(2hv/cm-1):
72977(7.9.16)
b2 =
Ry(2hv/cm-1):
72977(7.9.16)
pix
Gr:48, Lay:35
Gr:54, Lay:41
angul.d. 

113. C79Br+ pix Ry(2hv/cm-1): 78370(12.9.16) To top b2 =0.059484
Gr:49, Lay:36
Gr:54, Lay:41
angul.d. 

114. C79Br+ CBr+ KER broad peaks b2 To top
Gr:50

115. Comparison of CH3 and CH2 KERs
Pavle in and ,
See slides 116 – 125:

116. 66019 cm-1 ( nm)  
CH3
CH2

117. 66503 cm-1 ( nm)  
CH3
CH2

118. 67275 cm-1 ( nm)
CH3
CH2

119. 68684 cm-1 ( nm)
CH3
CH2

120. 72977 cm-1 ( nm)
CH3
CH2

121. 74249 cm-1 ( nm)
CH3
CH2

122. 75905 cm-1 ( nm)
CH3
CH2

123. 77165 cm-1 ( nm)
CH3
CH2

124. 78370 cm-1 ( nm)
CH3
CH2

125. 79610 cm-1 ( nm)
CH3
CH2

126. 66019 cm-1 ( nm)  
CH3
CH2

127. 66503 cm-1 ( nm)  
CH3
CH2

128. 67275 cm-1 ( nm)
CH3
CH2

129. 68684 cm-1 ( nm)
CH3
CH2

130. Possible explanation for the similarities:
CH2+ + e- + HBr
CH3++ e- + Br/Br*
Angular distribution
determining process:
1hni
1hni (?)
CH3Br#
1hnpd
1hnpd
CH3** + Br/Br*
CH2** + HBr ?
Dissociation
involves
one
bond break:
C-Br
Dissociation
involves
effective „one
bond break“:
C-H and C-Br
broken and
H-Br formed
CH3Br**
2hnr
The energetics is being
investigated by Arnar (170825)
CH3Br

131. As a matter of fact the images/angular distributions/b2 values for CH+ also resemble
those for CH3+ and CH2+ :
Thus, for example next slide.
We might therefore also have a common excitation (2hnr + 1hnpd) process to form
CH or CH* or CH** prior to photoionization, for example (?): CH3Br# -> (CH/CH*/CH**) + H2 + Br followed by (CH/CH*/CH**) + mhn -> CH+ + e-
NB: the ion intensities of vary as CH+ < CH2+ < CH3+ according to Mass resolved REMPI:
The energetics needs to
be checked

132. CH3+ b2
CH2+
CH+

133. Furthermore: it has been argured:
„C(3 P) and C*(1 D) atom and HBr intermediate production, detected by (2+1) REMPI,
most probably is due to photodissociation of CH3Br via two-photon excitations to Rydberg
states followed by an unusual breaking of four bonds and formation of two bonds to give
the fragments H2 + C/C* + HBr prior to ionization.”
See: