1. CH3I VMI-REMPI data and analysis:
Content pages: Plan-table and fig.………………………………………………………………………… 2-3
Figs. From Pavle:………………………………………………………………………… 4-9
CH3+, KERs, images and threshold predictions:…………………………
CH2+, KERs, and threshold predictions:…………………………
I+, KERs, and threshold predictions:……………………………… 29-36
e- PES´s, and threshold predictions…… ……
Conclusive remarks:……………………………………………………………………….. 56
From the literature(energetics of CH3)…………………………………………
Energetics:…………………………………………………………………………………… 61-65
Updated:

2. VMI-REMPI experimental plan:
CH3I:
no.
2hv/ eV
2hv/cm-1
1hv/cm-1
l / nm(1hv)
Rydberg state
converging to
ref:
Comment
Predicted /
6.777
6s(0,..)
2E1/2
Table 4* 1
6.906
6s (1/2) +v2
2E1/2 $
Table 5*
Not accessable by MOPO; use dye laser 2
7.306
6p (0…) #
2E3/2
Try use MOPO 3
7.36
6p(3/2) +v3
Table 6 * 4a 4b
7.381
(?)
Unassigned peak, relatively strong (?) 4c 5
7.402
6p(3/2) +nv6 6
7.642
6p(3/2) +nv1 7
7.82
5d(0,…) # 8
7.996
6p(0,…) # 9
8.022
7s(0,…) # 10
8.299
7s(3/2) +nv2
Table 6* 11
8.429
7p(0,…) #
(Try use MOPO); used exc./dye 12
8.652
i.e. 6 fundamental (0,…) bands (#); 5 vibrational bands; 1 uncertain band(?) / three bands for convergence to 2E1/2 ($)
*ref: ;
; sheet: Ry spectra

3. (4)
(2)
(12)
(6)
(11)
(10)
(0)
(7)
(3)
(8)
(9)
(1)

4. CH3+ KERs… and predictions I+ KERs……… and predictions
Figs from Pavle:
CH3+ KERs… and predictions
I+ KERs……… and predictions
PES´s………… and predictions
See :

5. KER for CH3+ from Pavle; Fig. from OriginPro 8.5 eV 170919 (2) 7.306
6p (0…) #
2E3/2
from Pavle;
Fig. from OriginPro 8.5 eV

6. , CH3I at nm, CH3

7. 20-09-2017, CH3I at 358.835 nm, I fragments, irises low

8. NB: thresholds obtained for D(CH3-I)=2.476 eV (PC; CRC)
7.306
6p (0…) #
2E3/2
Ideas from Pavle;
Fig. from OriginPro 8.5
Also in:
; sheet: Predictions
NB: thresholds obtained for
D(CH3-I)=2.476 eV (PC; CRC) eV

9. 20-09-2017, CH3I at 358.835 nm, photoelectrons
From PC..…CH3I results.ppt in

10. CH3+ KERs, images and
threshold predictions:

11. eV CH3+ KERs, Off resonance resonance resonance
170928
(1)
6.906
6s (1/2) +v2
2E1/2 $
Off resonance
(1)
6.906
6s (1/2) +v2
2E1/2 $
170920
resonance
resonance eV
For E(M+,eV) = 3.5e-5 x (pix)2
;Lay18,Gr19
; sheets: Ry spectra

12. eV CH3+ KERs, For E(M+,eV) = 3.5e-5 x (pix)2 MOPO 170919 (2) 7.306
6p (0…) #
2E3/2
170929
(2)
7.306
6p (0…) #
2E3/2
exc./dye eV
For E(M+,eV) = 3.5e-5 x (pix)2
;Lay19,Gr20
; sheets: Ry spectra

13. eV CH3+ KERs, For E(M+,eV) = 3.5e-5 x (pix)2
171003; (4a); (exp.)
171019; (4a); (exp.) less space charge effect eV
For E(M+,eV) = 3.5e-5 x (pix)2
;Lay31,Gr34
; sheets: Ry spectra

14. eV CH3+ KERs, Abel converted; file: „abel_speed“
170925
(11)
8.429
7p(0,…) #
2E3/2
Abel converted; file: „abel_speed“
NOT Abel converted; file: „x_speed“
171020
(11)
7p(0,…) #
2E3/2 eV
For E(M+,eV) = 3.50e-5 x (pix)2
;Lay12,Gr13
; sheets: Ry spectra

15. eV CH3+ Prediction calc: polarizer not IN Possibly:
(12)
8.652
7s(0,…) #
2E1/2 $
polarizer not IN
Prediction calc:
Possibly:
CH3I + 1hvpd -> CH3I*
CH3I* -> CH3#(..vi=1..)+ I;
CH3#(..vi=1..)+ 3hvi -> CH3+ + e-
i.e. (1pd + 3i) REMPI
CH3#(..vi=1..): vibrationally excited
NB: thresholds obtained for
D(CH3-I)=2.38 eV (AK)
Threshold for
CH3I + 1hvpd -> CH3I*
CH3I* -> CH3 (0,0,..+ I*
CH3 (0,..) + 3hvi -> CH3+ + e-
i.e. (1pd + 3i) REMPI eV
Threshold for
CH3I + 1hvpd -> CH3I*
CH3I* -> CH3 (0,0,..+ I
CH3 (0,..) + 3hvi -> CH3+ + e-
i.e. (1pd + 3i) REMPI eV
Subscript notations:
pd = photodissociation
i= ionization
DE = 0.33 eV / 2662 cm-1(?) eV
For E(M+,eV) = e-5 x (pix)2
;Lay7,Gr7
; sheet: Predictions

16. eV CH3+ KERs, updated: 170926 Off resonance see also slide 6
286.6 (exp.)
170922; (12)
8.652
7s(0,…) #
2E1/2 $
(exp.)
see also slide 6
above (PG)
for predictions eV
For E(M+,eV) = 3.50e-5 x (pix)2
;Lay13,Gr15
; sheet: Ry spectra

17. eV CH3+ KERs, Thresholds: i=2(3p2A2) i=1(3s2A1´ CH3**(i) + I*
170920
(1)
6.906
6s (1/2) +v2
2E1/2 $
170919
(2)
7.306
6p (0…) #
2E3/2
CH3**(i) + I*
NB: thresholds obtained for
D(CH3-I)=2.476 eV (PC;CRC)
CH3**(i) + I
i=2(3p2A2)
i=4(3d2A1´)
i=3(3d2E)
i=1(3s2A1´
CH3**(i) + I*
i=1(3s2A1´
i=2(3p2A2)
CH3**(i) + I
i=1(3s2A1´ eV
For E(M+,eV) = e-5 x (pix)2
;Lay2,Gr3
; sheets: Ry spectra & Predictions

18. eV CH3+ KERs, Thresholds: i=2(3p2A2) i=1(3s2A1´ CH3**(i) + I*
170920
(1)
6.906
6s (1/2) +v2
2E1/2 $
170919
(2)
7.306
6p (0…) #
2E3/2
CH3**(i) + I*
NB: thresholds obtained for
D(CH3-I)=2.38 eV (AK)
CH3**(i) + I
i=2(3p2A2)
i=4(3d2A1´)
i=3(3d2E)
i=1(3s2A1´
CH3**(i) + I*
i=1(3s2A1´
i=2(3p2A2)
CH3**(i) + I
i=1(3s2A1´ eV
For E(M+,eV) = e-5 x (pix)2
;Lay2,Gr3
; sheets: Ry spectra & Predictions

19. NB: The polarizer was not inserted in
CH3+ images:
Ry(2), (170920); nm(exp.) <= x1_10fl (RAW file)
Ry(12), ; nm(exp.) <= x1_5fl (RAW file)
Ry(1), ; nm(exp.) <= x1_5fl (RAW file)
NB: The polarizer was not inserted in
the exp., hence, the angul. distrib.
is invalid
Rings might be because of 1hvpd
channel(?)i.e.:

20. eV CH3+ KERs, : Virtually no difference 170920 (1) 359.062394
170919
(2)
6p (0…) #
2E3/2
171002 :
(3)
6p(3/2) +v3
2E3/2
171003; (4a); (exp.)
171003; (4b); (exp.)
171004; (4c); (exp.)
171005; (7); (exp.)
171006; (8); (exp.)
170925
(11)
7p(0,…) #
2E3/2
NO polarizer in
170921; (12)
7s(0,…) #
2E1/2 $
170922; (12)
7s(0,…) #
2E1/2 $ eV
Virtually no
difference
;Lay6,Gr8
For E(M+,eV) = e-5 x (pix)2for (1),(2) and (12)
For E(M+,eV) = 3.50e-5 x (pix)2 for (12) and (11), (3),(4a),4b,4c,7,8
; sheet: Ry spectra

21. eV CH3+ KERs, : Virtually no difference 170920 (1) 359.062394
170919
(2)
6p (0…) #
2E3/2
171002 :
(3)
6p(3/2) +v3
2E3/2
171003; (4a); (exp.)
171003; (4b); (exp.)
171004; (4c); (exp.)
171010; (6); (exp.)
171005; (7); (exp.)
171006; (8); (exp.)
171011; (9c); (exp.)
171020
(11)
7p(0,…) #
2E3/2
170922; (12)
7s(0,…) #
2E1/2 $ eV
Virtually no
difference
;Lay6,Gr8
For E(M+,eV) = e-5 x (pix)2for (1),(2) and (12)
For E(M+,eV) = 3.50e-5 x (pix)2 for (12) and (11), (3),(4a),4b,4c,7,8,6,9c
; sheet: Ry spectra

22. CH3+ KERs
Comparison of shifted spectra:
D(1hv) comparison
Likely channels………………………. 22
D(3hv) comparison

23. D1hv / eV CH3+ KERs, Common thresholds for
CH3I+1hv -> CH3 (X,v1v2v3v4)+I/I*:
NO FITS!
170920
(1)
6s (1/2) +v2
2E1/2 $
170919
(2)
6p (0…) #
2E3/2
171002 :
(3)
6p(3/2) +v3
2E3/2
171003; (4a); (exp.)
171003; (4b); (exp.)
171004; (4c); (exp.)
170925
(11)
7p(0,…) #
2E3/2
170922; (12)
7s(0,…) #
2E1/2 $
Virtually no
difference
D1hv / eV
;Lay26,Gr26
For E(M+,eV) = e-5 x (pix)2for (1),(2) and (12)
For E(M+,eV) = 3.50e-5 x (pix)2 for (12) and (11), (3),(4a),4b,4c
; sheet: Ry spectra; Predictions-short

24. D1hv / eV Common thresholds for CH3+ KERs,
CH3I+(3/2,1/2)+1hvpd -> CH3++ I/I*:
CH3I+(3/2); I*
CH3I+(1/2); I*
CH3I+(3/2); I
CH3I+(1/2); I
interpretation
Likely
170920
(1)
6s (1/2) +v2
2E1/2 $
170919
(2)
6p (0…) #
2E3/2
171002 :
(3)
6p(3/2) +v3
2E3/2
171003; (4a); (exp.)
171003; (4b); (exp.)
171004; (4c); (exp.)
171005; (7); (exp.)
170925
(11)
7p(0,…) #
2E3/2
170922; (12)
7s(0,…) #
2E1/2 $
Virtually no
difference
D1hv / eV
;Lay28,Gr28
For E(M+,eV) = e-5 x (pix)2for (1),(2) and (12)
For E(M+,eV) = 3.50e-5 x (pix)2 for (12) and (11), (3),(4a),4b,4c,7
; sheet: Ry spectra; Predictions-short

25. D3hv / eV CH3+ KERs, Common thresholds for
CH3I+3hv -> CH3 **(Ry,0000)+I/I*:
CH3 **(3p2A2)
CH3 **(3p2A2)
170920
(1)
6s (1/2) +v2
2E1/2 $
170919
(2)
6p (0…) #
2E3/2
171002 :
(3)
6p(3/2) +v3
2E3/2
Could be vibrational
structure
In the CH3**(3p2A2) + I
Channel (?); however peaks
do not match and PES spectra
suggest that CH3**
formation is not important.
See slide 43
171003; (4a); (exp.)
171003; (4b); (exp.)
171004; (4c); (exp.)
170925
(11)
7p(0,…) #
2E3/2
170922; (12)
7s(0,…) #
2E1/2 $
Virtually no
difference
D3hv / eV
;Lay27,Gr27
For E(M+,eV) = e-5 x (pix)2for (1),(2) and (12)
For E(M+,eV) = 3.50e-5 x (pix)2 for (12) and (11), (3),(4a),4b,4c
; sheet: Ry spectra; Predictions-short

26. CH2+ KERs:

27. eV CH2+ KERs, For E(M+,eV) = 3.41407e-5 x (pix)2 (1) 6.906 55700.63
6s (1/2) +v2
2E1/2 $ eV
;Lay3,Gr4
For E(M+,eV) = e-5 x (pix)2
; sheet: Ry spectra

28. eV CH2+ KERs, Z: Space charge NO Space charge Z: See PG PPT file on
170920
(1)
6s (1/2) +v2
2E1/2 $
171019
(1)
6s (1/2) +v2
2E1/2 $
See PG
PPT file on
Images and KERs the KERs don´t
seem to agree(?)
170929
(2)
(exp.)
6p (0…) #
2E3/2
171013
(2)
(exp.)
6p (0…) #
2E3/2 eV
(1): For E(M+,eV) = 3.5e-5 x (pix)2 & e-5 x (pix)2
(2):For E(M+,eV) = 3.5e-5 x (pix)2
;Lay3,Gr4
; sheet: Ry spectra

29. I+ KERS and
threshold predictions:

30. eV iris low I+ KERs, iris open Very high energy I+:
(1)
6.906
6s (1/2) +v2
2E1/2 $
iris low
Very high energy I+:
Prediction calc. for CH3 + I/I* formation
after 2hv, 3hv and 4hv could not predict these!
See:
; sheet: Predictions eV
;Lay4,Gr5
For E(M+,eV) = e-5 x (pix)2
; sheet: Ry spectra

31. eV iris low I+ KERs, updated: 170929 Off resonance iris open
(1)
6.906
6s (1/2) +v2
2E1/2 $
170928
170920
(1)
6.906
6s (1/2) +v2
2E1/2 $
iris low
iris open eV
For E(M+,eV) = 3.50e-5 x (pix)2
;Lay16,Gr17
; sheet: Ry spectra

32. eV I+ KERs, updated: 170926 Off resonance
286.6 (exp.)
170922; (12)
8.652
7s(0,…) #
2E1/2 $
Off resonance
(exp.) eV
For E(M+,eV) = 3.5e-5 x (pix)2
;Lay14,Gr14
; sheet: Ry spectra

33. eV I+ KERs, identical For E(M+,eV) = 3.5e-5 x (pix)2
171010; (9c); (exp.)
171010; (9); (exp.)
identical eV
For E(M+,eV) = 3.5e-5 x (pix)2
;Lay30,Gr30
; sheet: Ry spectra

34. eV I+ KERs, Looks like I resonance(?) ?
171024; (0); (exp.)
170920
(1)
6s (1/2) +v2
2E1/2 $
(2)
6p (0…) #
2E3/2
170919
I* ->-> I** OK; iodine resonance
171002
(3)
6p(3/2) +v3
2E3/2
171003; (4a); (exp.)
171004; (4b); (exp.)
171004; (4c); (exp.)
171010; (6); (exp.)
171005; (7); (exp.)
171006; (8); (exp.)
171010; (9); (exp.)
171020; (10); (exp.) eV
170925
(11)
7p(0,…) #
2E3/2
170922; (12)
7s(0,…) #
2E1/2 $
;Lay9,Gr10
For E(M+,eV) = 3.5e-5 x (pix)2
; sheet: Ry spectra

35. I+ KERs
Comparison of shifted spectra:
D(3hv) comparison

36. D3hv / eV I+ KERs Comparison on a D3hv scale:
Joined thresholds for : CH3I + 3hv -> CH3I# -> CH3 + I**;
for the lowest energy I**
171024; (0); (exp.)
170920
(1)
6s (1/2) +v2
2E1/2 $
(2)
6p (0…) #
2E3/2
170919
(3)
6p(3/2) +v3
2E3/2 :
171002
171004; (4b); (exp.)
171010; (6); (exp.)
171005; (7); (exp.)
170925
(11)
7p(0,…) #
2E3/2
170922; (12)
7s(0,…) #
2E1/2 $
D3hv / eV
;Lay25,Gr25
For E(M+,eV) = 3.5e-5 x (pix)2
; sheet: Ry spectra & Predictions-short

37. PES´s and
Threshold predictions:

38. eV PES, CH3**+ 1hv -> CH3+ CH3(X) + 3hv -> CH3+(X(1/2))
170920
(1)
6.906
6s (1/2) +v2
2E1/2 $
CH3**(3p2A2)+ 1hv -> CH3+
CH3I(X) + 3hv -> CH3I+
I(1/2)+ 3hv -> I+
CH3**(3s2A1´)+ 2hv -> CH3+ eV
;Lay11,Gr12
For E(M+,eV) = 3.29e-5 x (pix)2
; sheet: Predictions

39. eV PES, Off resonance For E(M+,eV) = 3.29e-5 x (pix)2 170928 (1) 6.906
6s (1/2) +v2
2E1/2 $
Off resonance
(1)
6.906
6s (1/2) +v2
2E1/2 $
170920 eV
;Lay17,Gr18
For E(M+,eV) = 3.29e-5 x (pix)2
; sheet: Ry spectra

40. eV PES, (2) Abs. CH3I + 2hvr -> CH3I**(6p(0..),2E3/2)
CH3I**(6p(0..),2E3/2) + hvpd -> CH3I#
CH3I# -> CH3**((2);3p 2A2) + I/I*
CH3**((2);3p 2A2) + hvi -> CH3+ + e-
i.e. (2r + 1pd + 1i) REMPI
NB: Threshold obtained for
D(CH3-I) = 2.38 eV
(2)
7.306
6p (0…) #
2E3/2 eV
For E(e-,eV) = 3.29e-5 x (pix)2
;Lay0,Gr1
; sheet: „Ry spectra“ & „Predictions“

41. eV PES, (2) Abs. For E(e-,eV) = 3.29e-5 x (pix)2 MOPO (2) 7.306
170919
(2)
7.306
6p (0…) #
2E3/2
170929
(2)
7.306
6p (0…) #
2E3/2
exc./dye eV
For E(e-,eV) = 3.29e-5 x (pix)2
;Lay20,Gr21
; sheet: „Ry spectra“

42. eV PES, CH3**(3s2A1´) + 1hv -> CH3+ CH3**(3p2A2) + 1hv -> CH3+
I(3/2)+ 3hv -> I+
170922; (12)
8.652
7s(0,…) #
2E1/2 $
Does not seem to fit any peaks
Suggests that CH3** formation is not
Important. See also slide 40 below. eV
;Lay10,Gr11
For E(M+,eV) = 3.29e-5 x (pix)2
; sheet: Predictions

43. eV PES, updated: 170926 Off resonance For E(M+,eV) = 3.29e-5 x (pix)2
170922; (12)
8.652
7s(0,…) #
2E1/2 $
(exp.) eV
;Lay15,Gr16
For E(M+,eV) = 3.29e-5 x (pix)2
; sheet: Ry spectra

44. eV PES, : ? Look the same 171024; (0); 366.025(exp.) 170920 (1)
6s (1/2) +v2
2E1/2 $
170919
(2)
6p (0…) #
2E3/2
171002
(3)
6p(3/2) +v3
2E3/2 :
171003; (4a); (?)
171004; (4b); (exp.)
171004; (4c); (exp.) (??)
? Look the same
171010; (6); (exp.)
171005; (7); (exp.)
171006; (8); (exp.)
171020; (10); (exp.)
170925
(11)
7p(0,…) #
2E3/2
170922; (12)
7s(0,…) #
2E1/2 $ eV
;Lay5,Gr6
For E(M+,eV) = 3.29e-5 x (pix)2 for all except:
For E(M+,eV) = 3.104e-5 x (pix)2 for (6), (10),(0)
; sheet: Ry spectra

45. eV PES, 171011; (9b); 309.11(exp.) 171011; (9a); 309.11(exp.)
171010; (9c); (exp.)
171006; (8); (exp.) eV
For E(e,eV) = 3.29e-5 x (pix)2 for (8):
;Lay29,Gr29
For E(e,eV) = 3.187e-5 x (pix)2 for (9,9a,9b,9c)
; sheet: Ry spectra

46. eV PES, Thresholds: 1hv for: For E(M+,eV) = 3.29e-5 x (pix)2
CH3I(Ry(2)) + 1hv -> CH3I+(3/2,1/2)+e
CH3I(Ry(1)) + 1hv -> CH3I+(3/2,1/2)+e
(11): 2,5 & 3.1 eV (no fit)
(12): 2.8 & 3.4 eV (no fit)
-which equals that for 3hv excitation via
The Rydb. States to for CH3I+(3/2) and
CH3I+(1/2)
170920 1
6.906
6s (1/2) +v2
2E1/2 $
170929 2
7.306
6p (0…) #
2E3/2
170925
(11)
8.429
7p(0,…) #
2E3/2
170922; (12)
8.652
7s(0,…) #
2E1/2 $ eV
;Lay21,Gr22
For E(M+,eV) = 3.29e-5 x (pix)2
; sheet: Ry spectra & Predictions-short

47. Comparison of shifted PES´s
D(1hv) comparison
D(3hv) comparison
Discussion

48. Good matching of peaks => 1hv ionization processes
PES, (on a D1hv scale)
No good fits
of thresholds:
Ionization of
CH3** not
important
Thresholds: 1hv
Processes for
CH3**(i;0..) + hv ->
CH3+ + e
i= 1-6
170920 1
6.906
6s (1/2) +v2
2E1/2 $ 2
7.306
6p (0…) #
2E3/2
170929
171002
(3)
7.36
6p(3/2) +v3
2E3/2
170925
(11)
8.429
7p(0,…) #
2E3/2 12
8.652
7s(0,…) #
2E1/2 $
170922
Good matching of peaks =>
1hv ionization processes
are largely involved
D1hv / eV
;Lay24,Gr24
For E(M+,eV) = 3.29e-5 x (pix)2
; sheet: Ry spectra & Predictions-short

49. The various thresholds above are:
No good fits
of thresholds:
Ionization of
CH3** not
important
Let´s consider if the 1hv excitation channels are consistent with
I** + 1hv -> I+ + e; I**: Rydberg states of iodine atoms
NB: I+ ion signals are strong according to mass spectra.
; sheet: Predictions-short

50. D1hv / eV PES, (on a D1hv scale) Thresholds for I** + hv -> I+ + e:
170920
(1)
6s (1/2) +v2
2E1/2 $
170919
(2)
6p (0…) #
2E3/2
171002 :
(3)
6p(3/2) +v3
2E3/2
171004; (4b); (exp.)
171005; (7); (exp.)
171006; (8); (exp.)
170925
(11)
7p(0,…) #
2E3/2
170922; (12)
7s(0,…) #
2E1/2 $
For E(M+,eV) = 3.29e-5 x (pix)2
D1hv / eV
;Lay24,Gr24
; sheet: Ry spectra & Predictions-short

51. D1hv / eV PES, (on a D1hv scale) Thresholds for I** + hv -> I+ + e:
171024; (0); (exp.)
170920
(1)
6s (1/2) +v2
2E1/2 $
(2)
6p (0…) #
2E3/2
170919 :
171002
(3)
6p(3/2) +v3
2E3/2
171004; (4b); (exp.)
171010; (6); (exp.)
171005; (7); (exp.)
171006; (8); (exp.)
170925
(11)
7p(0,…) #
2E3/2
170922; (12)
7s(0,…) #
2E1/2 $
D1hv / eV
For E(e,eV) = 3.29e-5 x (pix)2
Except: For E(e,eV) = 3.154e-5 x (pix)2 for (8) and (6) E(e,eV) = 3.104e-5 x (pix)2 for (0)
;Lay24,Gr24
; sheet: Ry spectra & Predictions-short

52. D1hv / eV Thresholds for PES, (on a D1hv scale) I** + hv -> I+ + e:
I**(5s25p4(3P1)6s; J=3/2) + hv -> I+ + e 
I**(5s25p4(3P2)6s; J =5/2 ) +hv-> I+ +e 
I**(5s25p4(3P2)6s; J =3/2 ) +hv-> I+ +e 
170920
(1)
6s (1/2) +v2
2E1/2 $
170919
(2)
6p (0…) #
2E3/2
171002 :
(3)
6p(3/2) +v3
2E3/2
171004; (4b); (exp.)
171010; (6); (exp.)
171005; (7); (exp.)
171006; (8); (exp.)
170925
(11)
7p(0,…) #
2E3/2
170922; (12)
7s(0,…) #
2E1/2 $
D1hv / eV
For E(M+,eV) = 3.29e-5 x (pix)2
Except: For E(M+,eV) = 3.154e-5 x (pix)2 for (8) and (6)
;Lay24,Gr24
; sheet: Ry spectra & Predictions-short

53. D3hv / eV PES, (on a D3hv scale) : I+ <- I(3/2) I+ <- I(1/2):
CH3I+(1/2;0,0,0,0,1,0) <- CH3I(X;0,..)
I+ <- I(3/2)
CH3I+(3/2;0..) <- CH3I(X;0..)
CH3I+(1/2;0,0,0,0,0,0) <- CH3I(X;0,..)
CH3I+(3/2;0,0,0,0,1,0) <- CH3I(X;,0,…)
I+ <- I(1/2):
CH3+ <- CH3(X)
171024; (0); (exp.)
170920
(1)
6s (1/2) +v2
2E1/2 $
170919
(2)
6p (0…) #
2E3/2
171002
(3)
6p(3/2) +v3
2E3/2 :
171003; (4a)
170925
(11)
7p(0,…) #
2E3/2
170922; (12)
7s(0,…) #
2E1/2 $
D3hv / eV
;Lay22,Gr23
For E(e,eV) = 3.29e-5 x (pix)2
Except E(e,eV) = 3.104e-5 x (pix)2 for (0)
; sheet: Ry spectra

54. D3hv / eV PES, (on a D3hv scale) 3hv processes :
CH3I+(1/2;0,0,0,0,1,0) <- CH3I(X;0,..)
CH3I+(1/2;0,0,0,0,0,0) <- CH3I(X;0,..)
CH3I+(3/2;0,0,0,0,1,0) <- CH3I(X;,0,…)
CH3I+(3/2;0..) <- CH3I(X;0..)
I+ <- I(3/2)
I+ <- I(1/2)
CH3+ <- CH3(X)
171024; (0); (exp.)
170920
(1)
6s (1/2) +v2
2E1/2 $
170919
(2)
6p (0…) #
2E3/2 :
171002
(3)
6p(3/2) +v3
2E3/2
171003; (4a)
170925
(11)
7p(0,…) #
2E3/2
170922; (12)
7s(0,…) #
2E1/2 $
D3hv / eV
;Lay22,Gr23
For E(e,eV) = 3.29e-5 x (pix)2
Except E(e,eV) = 3.104e-5 x (pix)2 for (0)
; sheet: Ry spectra & Predictions-short

55. D(3hv) comparison / The various thresholds above are:
3.138
3.438
2.818
CH3+ formation from CH3(X):
by 3hv:
I+ formation from I(3/2):
I+ formation from I(1/2):
CH3I+(3/2;0,0,0,0,0,0) formation from CH3I(X;0,0,0,0,0,0) by 3hv:
CH3I+(3/2;0,0,0,0,1,0) formation from CH3I(X;,0,0,0,0,0,0) by 3hv:
CH3I+(1/2;0,0,0,0,0,0) formation from CH3I(X;0,0,0,0,0,0) by 3hv:
CH3I+(1/2;0,0,0,0,1,0) formation from CH3I(X;0,0,0,0,0,0) by 3 hv:
; sheet: Predictions-short

56. Preliminary conclusive remarks:
; sheet: D(nhv) comp.

57. From the literature:
CH3 energetics

58. X(CH3): Methyl Radical, CH3 Vibrational states of the ground
To top
X(CH3):
Methyl
Radical, CH3
Vibrational states
of the ground
electronic state

59. *3 *2 * CH3** *6 *5 *4 Methyl Radical, CH3 electronic state To top

60. http://webbook. nist. gov/cgi/cbook. cgi
X(CH3+):

61. Energetics:
CH3I photoexcitation

62. CH3**(i)+I*; i=1-6 CH3**(i)+I; i=1-6 no. 2hv/cm-1 Ry 1 55700.63 2
(n) = number of photons
CH3**(i)+I; i=1-6
CH3 + I+ + e;
no.
2hv/cm-1 Ry 1 2 3 4 5 6 7 8 9 10 11 12 i= 6 : 1
Abs. spectrum i= 6 : 1
CH3+ + e + I;
(4)
CH3I+ + e;
CH3 + I**(min);
70000
(3)
55000
(2)
CH3 + I*;
(1)
CH3 + I;
CH3I
; Layo,Gr0;
; sheet: Energetics

63. Abs. spectrum (n) = number of photons CH3 + I+ + e; 103491.0874 i= 6 :
CH3**(i)+I*; i=1-6
CH3**(i)+I; i=1-6
CH3 + I+ + e; i= 6 : 1
CH3+ + e + I;
Abs. spectrum i= 6 : 1
(4)
CH3 + I**
CH3I+ + e;
70000
CH3 + I**(min);
(3)
55000
(2)
CH3 + I*;
(1)
CH3 + I;
CH3I
; Layo,Gr0;
; sheet: Energetics

64. CH3I* -> CH3 (v1,v2,…) + I/I* CH3 (v1,v2,…) + 3hvi -> CH3+ + e-
(12)
8.652
7s(0,…) #
2E1/2 $
i.e.
CH3I + 1hvpd -> CH3I*
CH3I* -> CH3 (v1,v2,…) + I/I*
CH3 (v1,v2,…) + 3hvi -> CH3+ + e-
i.e. (1pd + 3i) REMPI

65. CH3**(i)+I*; i=1-6 CH3**(i)+I; i=1-6 no. 2hv/cm-1 Ry 1 55700.63 2
(12)
8.652
7s(0,…) #
2E1/2 $
CH3**(i)+I*; i=1-6
(n) = number of photons
CH3**(i)+I; i=1-6
CH3 + I+ + e;
no.
2hv/cm-1 Ry 1 2 3 4 5 6 7 8 9 10 11 12 i= 6 : 1
Abs. spectrum i= 6 : 1
CH3+ + e + I;
(4)
CH3I+ + e;
CH3 + I**(min);
70000 close to 69783
(3)
55000
(2)
CH3 + I*;
(1)
CH3 + I;
CH3I
; Layo,Gr0;
; sheet: Energetics