CH3Br, one-color exp.: CHn+, iBr+ and CiBr+ ions vs CH3Br(Ry) states: https://notendur.hi.is/~agust/rannsoknir/Crete16/PPT-160908-CH3Br(2).pptx Content: pages:

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CH3Br, one-color exp.: CHn+, iBr+ and CiBr+ ions vs CH3Br(Ry) states: https://notendur.hi.is/~agust/rannsoknir/Crete16/PPT-160908-CH3Br(2).pptx 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 …………………………………………………………………………………. 7-16 CH3+ interpretation ………………….…………………………………………………………………… 18-19 CH2+; KERs and images …………………………………………………………………………………. 20-24 CH+; KERs ……………………………………………………………………………………………………… 25-26 79Br + ; KERs and images ..………………………………………………………………………………. 27-31 C79Br + ;KERs …………………………………………………………………………........................... 32-33 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+………………………………………. 46-49 Comparison of C79Br+ and C81Br+(CH279Br+) signals for Ry(67275; 160913)……………………………………………………………………………………….. 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…………………………………. 65-68 Angular distributions: CH3+…………………………………….…………………………………………………………………….. 70-81 CH2+(under construction)………………………………………….………………………………………. 82-88 CH+………………………………….………………………………………….………………………………………. 89-96 Br+……………………………………………………………………………………………………………………... 97-106 CBr+…………………………………………………………………………………………………………………… 107-113 comparison of CH3+, CH2+ (and CH+, C+) signals………………………………………………… 115-132 Updated: 25.08.2017

KERs(xx): Ry(2hv/cm-1): CH3+ CH2+ CH+ C+ 72977(from 7.9.16) To top Ry(2hv/cm-1): 72977(from 7.9.16) 66019 (from 6.9.16) CH3+ CH2+ CH+ C+ eV https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160908.pxp; Gr:9, Lay:0 date: 08.09.2016

KERs(xx): Ry(2hv/cm-1): 72977(from 7.9.16) 79Br+ C79Br+ To top 0.0184 eV 0.111 eV Ry(2hv/cm-1): 72977(from 7.9.16) 66019 (from 6.9.16) 79Br+ C79Br+ Calc. energy for CH3 + Br (<= Arnar; 160908): 0.179eV Calc. energy for CH3 + Br*(<= Arnar; 160908): 0.108 eV 0.170 eV 0.0457 eV 81Br+ C79Br+ eV https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160908.pxp; Gr:10, Lay: 1 date: 08.09.2016

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 07.09.2016): 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: 08.09.2016

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: 08.09.2016

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 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160908a.pxp; Gr:9, Lay:0 date created: 09.09.2016

To top CH3+

KERs (xx): CH3+ eV Ry(2hv/cm-1): 78370(12.9.16) 77165(15.9.16) To top CH3+ Ry(2hv/cm-1): 78370(12.9.16) 77165(15.9.16) 75905(14.9.16) 74249(15.9.16) 72977(7.9.16) 68684(14.9.16) 67275(13.9.16)) 66503(8.9.16) 66019 (6.9.16) CH3+ +Br- eV https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:11, Lay:2 date created: 15.09.2016

KERs (xx): CH3+ eV Ry(2hv/cm-1): 78370(12.9.16) 77165(15.9.16) To top CH3+ Ry(2hv/cm-1): 78370(12.9.16) 77165(15.9.16) 75905(14.9.16) 74249815.9.16) 72973(7.9.16) 68684(14.9.16) 67275(13.9.16)) 66503(8.9.16) 66019 (6.9.16) CH3+ +Br- eV https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:11, Lay:2 date created: 15.09.2016

KERs (xx): CH3+ eV Ry(2hv/cm-1): 79610 (16.09.16) 78370(12.9.16) To top CH3+ Ry(2hv/cm-1): 79610 (16.09.16) 78370(12.9.16) 77165(15.9.16) 75905(14.9.16) 74249815.9.16) 72973(7.9.16) 68684(14.9.16) 67275(13.9.16)) 66503(8.9.16) 66019 (6.9.16) CH3+ +Br- eV https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:11, Lay:2 date created: 16.09.2016

CH3+ REMPI specttra (1/2)6p w = 2 0 5d (3/2)6d w = 2 0 To top https://notendur.hi.is/~agust/rannsoknir/Crete16/CH3Br REMPI spectra-160906.pxp

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 (15.09.16) 78339.2 (16.9.16) 78370(12.9.16) 78431.4 (16.9.16) 79610 (16.09.16) n =6; n2 n=7; w = 0; (3/2)np CH3+ +Br- n = 6 w = 2 0; (1/2)np n = 5; w = 2 0; (3/2)nd eV https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:27Lay:16 date created: 19.09.2016

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 (15.09.16) 78339.2 (16.9.16) 78370(12.9.16) 78431.4 (16.9.16) 79610 (16.09.16) n =6; n2 n=7; w = 0; (3/2)np CH3+ +Br- n = 6 w = 2 0; (1/2)np n = 5; w = 2 0; (3/2)nd eV https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:27Lay:16 date created: 19.09.2016

Images (xx): CH3+ CH3+ +Br- Ry(2hv/cm-1): 67275(13.9.16)) To top Ry(2hv/cm-1): 67275(13.9.16)) 66503(8.9.16) 66019 (6.9.16) CH3+ +Br- https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:11, Lay:2 date created: 14.09.2016

KERs (xx): CH3+ CH3+ +Br- Ry(2hv/cm-1): 74249(15.9.16) 72973(7.9.16) To top Ry(2hv/cm-1): 74249(15.9.16) 72973(7.9.16) 68684(14.9.16) CH3+ +Br- https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:11, Lay:2 date created: 14.09.2016

KERs (xx): CH3+ CH3+ +Br- Ry(2hv/cm-1): 78370(12.9.16) 77165(15.9.16) To top Ry(2hv/cm-1): 78370(12.9.16) 77165(15.9.16) 75905(14.9.16) https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:11, Lay:2 date created: 14.09.2016

KERs (xx): CH3+ eV Ry(2hv/cm-1): 66019 (6.9.16; MOPO) 66019 (07.10.16; Dye laser) To top CH3+ eV https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:44, Lay:31

Clear shift of peaks as 66019 -> 66503 To top CH3+: Clear shift of peaks as 66019 -> 66503 More peaks appear as 66019 -> 66503 Peak structure looks like vibrational structure Possible interpretation: Molecular excitation Dissoci- ation Fragment ionization CH3+ + 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

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

To top CH2+

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(16.9.16) 78370(12.9.16) 77165(15.9.16) 75905(14.9.16) 74249(15.9.16) 72973(7.9.16) 68684(14.9.16) 67275(13.9.16)) 66503(8.9.16) 66019 (6.9.16) CH3+ + Br- https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:12, Lay:3 date created: 15.09.2016

Images (xx): CH2+ CH3+ + Br- Ry(2hv/cm-1): 67275(13.9.16)) To top Ry(2hv/cm-1): 67275(13.9.16)) 66503(8.9.16) 66019 (6.9.16) CH3+ + Br- https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160914.pxp; Gr:12, Lay:3 date created: 15.09.2016

KERs (xx): CH2+ CH3+ + Br- Ry(2hv/cm-1): 75905(14.9.16 72973(7.9.16) To top Ry(2hv/cm-1): 75905(14.9.16 72973(7.9.16) 68684(14.9.16) CH3+ + Br- https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160914.pxp; Gr:12, Lay:3 date created: 14.09.2016

KERs (xx): CH2+ CH3+ + Br- Ry(2hv/cm-1): 78370(12.9.16) To top https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160914.pxp; Gr:12, Lay:3 date created: 15.09.2016

To top CH+

KERs (xx): CH+ Ry(2hv/cm-1): 78370(12.9.16) To top CH+ Ry(2hv/cm-1): 78370(12.9.16) 75905(14.9.16) 72977(7.9.16) 68684(14.9.16) 67273 (13.9.16) 66019 (6.9.16) CH3+ + Br- https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:23, Lay:12 date created: 15.09.2016

To top 79Br+

KERs (xx): 79Br+ Ry(2hv/cm-1): CH3+ + Br- 79610(16.9.16) To top 79Br+ Ry(2hv/cm-1): 79610(16.9.16) 78370(12.9.16) 77165(15.9.16) 75905(14.9.16) 72977(7.9.16) 68684(14.9.16) 67273 (13.9.16) 66019 (6.9.16) CH3+ + Br- https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:24, Lay:13 date created: 15.09.2016

KERs (xx): 79Br+ Ry(2hv/cm-1): 68684(14.9.16) 67273 (13.9.16) To top 79Br+ Ry(2hv/cm-1): 68684(14.9.16) 67273 (13.9.16) 66019 (6.9.16) CH3+ + Br- https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:24, Lay:13 date created: 15.09.2016

KERs (xx): 79Br+ Ry(2hv/cm-1): 78370(12.9.16) 75905(14.9.16) To top 79Br+ Ry(2hv/cm-1): 78370(12.9.16) 75905(14.9.16) 72977(7.9.16) CH3+ + Br- https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:24, Lay:13 date created: 15.09.2016

KERs (xx): 79Br+ Ry(2hv/cm-1): 79610(16.9.16) CH3+ + Br- To top https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:24, Lay:13

To top C79Br+

KERs (xx): C79Br+ Ry(2hv/cm-1): 78370(12.9.16) 72977(7.9.16) To top C79Br+ Ry(2hv/cm-1): 78370(12.9.16) 72977(7.9.16) 68684(14.9.16) 67273 (13.9.16) 66019 (6.9.16) CH3+ + Br- https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160914.pxp; Gr:25, Lay:14 date created: 14.09.2016

To top X vs Z data:

KERs (xx) & (zz): CH3+ eV Ry(2hv/cm-1): 66503(8.9.16) To top https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160908a.pxp; Gr:13, Lay:4 date created: 09.09.2016

KERs (xx) & (zz): CH3+ eV Ry(2hv/cm-1): 66019(6.9.16) To top https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160908a.pxp; Gr:13, Lay:4 date created: 09.09.2016

KERs (xx) & (zz): CH3+ eV Ry(2hv/cm-1): 77165(15.9.16) To top https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-1609015.pxp; Gr:28, Lay:17 date created: 20.09.2016

KERs (xx) & (zz): CH3+ eV Ry(2hv/cm-1): 79610(16.9.16) To top https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-1609015.pxp; Gr:29, Lay:18 date created: 20.09.2016

To top Energetics

Energetics with respect to possible CH3+ formation: To top Study range 66000-81000 cm-1 Energetics with respect to possible CH3+ formation: 33009 99029 66019 33009 r/A https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160909-energetics-CH3.pxp; Gr:0; Lay:0

Energetics with respect to possible CH3+ formation: To top Study range 66000-81000 cm-1 Energetics with respect to possible CH3+ formation: 2hn 1hn r/A https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; „various things“ https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-161003-energetics-CH3.pxp; Gr:0; Lay:0

NB: 2hv excitations 66019 – 68684 cm-1 < CH3**(3s 2A1) + Br/Br* 3hv excitations 66019 – 68684 cm-1 < CH3+ + Br/Br* 3hv excitations 72973 – 79610 cm-1 > CH3+ + Br/Br*

Energetics with respect to possible CH3+ formation To top Study range 66000-81000 cm-1 Energetics with respect to possible CH3+ formation And CH3 ionizations: 3hni 1hn r/A https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; „various things“ https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-161003a-energetics-CH3.pxp; Gr:0; Lay:0

NB: The 79610 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 (?)

To top refs in Theos, 2014 paper l/nm cm-1 year ref: Theo,2014 193 51813.4715 2014 https://notendur.hi.is/~agust/rannsoknir/papers/pccp16-599-14.pdf 2 215 to 251 39840 to 46512 1998 https://notendur.hi.is/~agust/rannsoknir/papers/jcp108-5742-98.pdf 3 193,222 45045, 51813 1985 https://notendur.hi.is/~agust/rannsoknir/papers/cp92-59-85.pdf 4 205 48780 1992 https://notendur.hi.is/~agust/rannsoknir/papers/cp163-277-92.pdf 5 213, ca.230 43478, 46948 2007 https://notendur.hi.is/~agust/rannsoknir/papers/jcp127-224310-07.pdf 6 216 46296 2009 https://notendur.hi.is/~agust/rannsoknir/papers/jcp130-034304-09.pdf 7 240 to 280 35714 to 41667 2000 https://notendur.hi.is/~agust/rannsoknir/papers/pccp1-747-00.pdf https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-161004-energetics-CH3.pxp; Gr:0; Lay:0 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; „1hv phd“

Energetics with respect to possible CH2+ formation: To top Study range 66000-81000 cm-1 Energetics with respect to possible CH2+ formation: 66019 33009 33009 99029 66019 33009 CH3**+Br r/A https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160909-energetics-CH2.pxp; Gr:0; Lay:0

To top Images vs. KERs:

Ry(78370); 255.233 nm; Date: 160912 CH3+ CH2+ CH+ KERs: eV To top https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160913.pxp Gr:17,Lay:6 Gr:18,Lay:7, Gr:19,Lay:8

Hint of a „shoulder“ from the „blob“ Ry(78370); 255.233 nm; Date: 160912 To top CH3+ CH2+ Hint of a „shoulder“ from the „blob“ eV https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160913.pxp Gr:17,Lay:9

Ry(78370); 255.233 nm; Date: 160912 79Br+ C79Br+ KERs: eV To top https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160913.pxp Gr:20,Lay:1; Gr:21, Lay:10

Comparison for C79Br+ and C81Br+(CH279Br+) signals for Ry(67275; 160913): To top Virtually identical eV https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160914.pxp; Gr:26, Lay:15 date created: 14.09.2016

2hvr: signals following Bands according to https://notendur.hi.is/~agust/rannsoknir/papers/jpcA112-7170-08.pdf (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 https://notendur.hi.is/~agust/rannsoknir/Crete16/CH3Br REMPI spectra-160906.pxp; Gr:0; Lay:0

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

3hv excitations 3Dhn/eV Thresholds 79610 (16.09.16) 78370(12.9.16) 77165(15.9.16) 75905(14.9.16) 74249815.9.16) Ry(2hv/cm-1) KERs: 72973(7.9.16) 68684(14.9.16) 67275(13.9.16)) 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 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; CH3;one-color https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-161028.pxp; Gr:61, Lay:45

1hv excitations Dhn/eV Thresholds Hot bands, i.e. due to 79610 (16.09.16) 78370(12.9.16) 77165(15.9.16) 75905(14.9.16) 74249815.9.16) Ry(2hv/cm-1) KERs: 72973(7.9.16) 68684(14.9.16) 67275(13.9.16)) 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# https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; CH3;one-color https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-161028.pxp; Gr:62, Lay:47

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 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-161028a.pxp; Gr:61, / * Gr:63 # f = 2.72 x 10-5; *f= 2.98x10-5

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* https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-161028a.pxp; Gr:62, / * Gr:64 # f = 2.72 x 10-5; *f= 2.98x10-5

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 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-161028a.pxp; Gr:63 *f= 2.98x10-5

1hv excitations eV* To top 68684(14.9.16) 67275(13.9.16)) 66503(8.9.16) 66019 (6.9.16) 1hv excitations eV* https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-161028a.pxp; Gr:63 *f= 2.98x10-5

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.

excitations 1hv DE/eV Thresholds 79610 (16.09.16) 78370(12.9.16) 77165(15.9.16) 75905(14.9.16) 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 = 1.8876 CH3(0000)+Br*(1.2016) CH3(0010)+Br (1.2562) b2 = 0.89093 b2 = 1.4666 CH3(1000)+Br(1.2725) b2 = -0.14974 CH3(0001)+Br(1.4394) b2 = -0.23585 CH3(0100)+Br(1.5224) CH3(0000)+Br(1.5856) b2 = 1.5678 DE/eV b2 = 1.0978 Thresholds b2 = 1.4741 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; CH3;one-color https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-161028.pxp; Gr:62, Lay:47

excitations 1hv DE/eV Thresholds corresponding to tranitions from Ry(2hv/cm-1) KERs: 77165 (15.09.16) 78339.2 (16.9.16) 78370(12.9.16) 78431.4 (16.9.16) 79610 (16.09.16) 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) https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; CH3;one-color https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:61, Lay:45

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

2hvr: signals following Ry(2hv/cm-1) KERs: To top Example of a 1hv and 1hvr signal contributions in a CH3 KER spectrum: 77165 (15.09.16) 1hv: Signals following one-photon excitation 2hvr: signals following two-photon resonance excitation eV https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:62, Lay:46

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 66019-68684_regarding vibrational ladder.pptx ;

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 66019-68684_regarding vibrational ladder.pptx ;

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 66019-68684_regarding vibrational ladder.pptx ;

Slide 9*: *….Dropbox/REMPI/From Arnar/CH3Br/Focus on first 4 peaks 66019-68684_regarding vibrational ladder.pptx ;

Slide 10*: *….Dropbox/REMPI/From Arnar/CH3Br/Focus on first 4 peaks 66019-68684_regarding vibrational ladder.pptx ;

To top Angular distributions: X files

To top CH3+:

CH3+ pix q Ry(2hv/cm-1): 66019(6.9.16) To top b2 = 1.3838 b2 = 1.2627 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:32, Lay:19 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:24, Lay:10 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

CH3+ pix q Ry(2hv/cm-1): 66503(8.9.16) To top b2 = 0.88204 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:33, Lay:20 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:24, Lay:11 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

CH3+ pix q Ry(2hv/cm-1): 67275(13.9.16) To top b2 = 1.1489 b2 = 1.1593 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:34, Lay:21 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:22, Lay:12 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

CH3+ pix q Ry(2hv/cm-1): 68684(14.9.16) To top b2 = 0.81842 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:35, Lay:22 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:26, Lay:13 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

CH3+ pix q Ry(2hv/cm-1): 72977(7.9.16) To top b2 = 2.0226 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:38, Lay:25 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:28, Lay:16 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

CH3+ pix q Ry(2hv/cm-1): 74249(15.9.16) To top b2 = 1.3393 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:37, Lay:24 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:27, Lay:15 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

CH3+ pix q Ry(2hv/cm-1): 75905(14.9.16) To top b2 = -0.049622 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:36, Lay:23 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:25, Lay:14 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

CH3+ X Z eV q Ry(2hv/cm-1): 77165(15.9.16) To top b2 = 1.0978 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:20, Lay:8 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx

CH3+ X Z eV q Ry(2hv/cm-1): 79610(16.9.16) To top b2 = 1.4741 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:19, Lay:7 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx

CH3+ https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:11, Lay:2 To top https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:21, Lay:9 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx

CH3+ 1.2932 66019 0.71411 66503 1.1593 67275 0.71876 68684 2.0226 72977 1.3393 74249 -0.058 75905 0.5568 77165 0.2957 78370 0.0092239 79610 To top b2 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp; Gr:47

To top CH2+: Under construction

CH2+ pix q Ry(2hv/cm-1): 66019(6.9.16) To top b2 = 2.0185 b2 = 1.7032 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:40, Lay:27 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:50, Lay:37 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

CH2+ pix q Ry(2hv/cm-1): 66503(8.9.16) To top b2 = 1.0753 b2 = 1.0054 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:41, Lay:28 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:51, Lay:38 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

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 = 0.83254 pix q https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:42, Lay:29 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:52, Lay:39 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

CH2+ pix q Ry(2hv/cm-1): 68684(14.9.16) To top b2 = 1.7498 b2 = 1.4938 1.3614 b2 = 1.2734 pix b2 = 0.983565 q https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:43, Lay:30 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:53, Lay:40 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

CH3+ To top b2 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:58

CH2+ To top b2 increases with KER, i.e. Parallel character increases with KER -for all the Ry resonances (66019 – 68684 cm-1)

To top CH+:

CH+ pix Ry(2hv/cm-1): 66019 (6.9.16) To top b2 = 2.1339 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:51, Lay:37 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:55, Lay:42 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

CH+ pix Ry(2hv/cm-1): 67275 (13.9.16) To top b2 = 1.2698 b2 = 1.3594 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:52, Lay:38 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:55, Lay:42 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

CH+ pix Ry(2hv/cm-1): 68684(14.9.16) To top b2 = 1.5498 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:53, Lay:39 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:55, Lay:42 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

CH+ pix Ry(2hv/cm-1): 72977(7.9.16) Ry(2hv/cm-1): 72977(7.9.16) To top b2 = 1.7778 Ry(2hv/cm-1): 72977(7.9.16) pix https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:54, Lay:40 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:55, Lay:42 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

CH+ pix Ry(2hv/cm-1): 75905(14.9.16) To top b2 = 1.1067 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:55, Lay:41 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:55, Lay:42 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

CH+ pix Ry(2hv/cm-1): 78370(12.9.16) To top b2 = 0.9554 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:56, Lay:42 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:55, Lay:42 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

CH+ To top b2 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:57

To top Br+:

Br+ pix q Ry(2hv/cm-1): 66019 (6.9.16) To top b2 = 2.2123 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:38, Lay:26 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

Br+ pix q Ry(2hv/cm-1): 67273 (13.9.16) To top b2 = 1.553 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:37, Lay:25 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

Br+ pix q Ry(2hv/cm-1): 68684(14.9.16) To top b2 = 1.5328 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:36, Lay:24 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

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 = 1.8499 Ry(2hv/cm-1): 72977(7.9.16) pix q https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:29, Lay:17 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

Br+ pix q Ry(2hv/cm-1): 75905(14.9.16) To top b2 = 1.1844 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:39, Lay:27 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

Br+ pix q Ry(2hv/cm-1): 77165(15.9.16) To top b2 = 1.1202 b2 =0.65639 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:35, Lay:23 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

Br+ pix q Ry(2hv/cm-1): 78370(12.9.16) To top b2 = 1.2279 b2 =1.0963 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:34, Lay:22 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

Br+ pix q Ry(2hv/cm-1): 79610(16.9.16) To top b2 =1.28 b2 =1.0372 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:33, Lay:21 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

Br+ Br+ Low KER broad peak b2 To top https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160921.pxp; Gr:58

To top C79Br+

C79Br+ pix Ry(2hv/cm-1): 66019 (6.9.16) To top b2 =0.59096 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:45, Lay:32 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:54, Lay:41 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

C79Br+ pix Ry(2hv/cm-1): 67273 (13.9.16) To top b2 =0.09929 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:46, Lay:33 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:54, Lay:41 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

C79Br+ pix Ry(2hv/cm-1): 68684(14.9.16) To top b2 =0.18756 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:47, Lay:34 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:54, Lay:41 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

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 =0.23221 Ry(2hv/cm-1): 72977(7.9.16) pix https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:48, Lay:35 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:54, Lay:41 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

C79Br+ pix Ry(2hv/cm-1): 78370(12.9.16) To top b2 =0.059484 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:49, Lay:36 https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160920-ad.pxp, Gr:54, Lay:41 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; angul.d.

C79Br+ CBr+ KER broad peaks b2 To top https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-160915.pxp; Gr:50

Comparison of CH3 and CH2 KERs Pavle in and e-mail, 161221 See slides 116 – 125:

66019 cm-1 (303.000 nm) CH3 CH2

66503 cm-1 (300.318 nm) CH3 CH2

67275 cm-1 (297.324 nm) CH3 CH2

68684 cm-1 (291.231 nm) CH3 CH2

72977 cm-1 (274.140 nm) CH3 CH2

74249 cm-1 (269.394 nm) CH3 CH2

75905 cm-1 (263.550 nm) CH3 CH2

77165 cm-1 (259.232 nm) CH3 CH2

78370 cm-1 (255.230 nm) CH3 CH2

79610 cm-1 (251.279 nm) CH3 CH2

66019 cm-1 (303.000 nm) CH3 CH2

66503 cm-1 (300.318 nm) CH3 CH2

67275 cm-1 (297.324 nm) CH3 CH2

68684 cm-1 (291.231 nm) CH3 CH2

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

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

CH3+ b2 CH2+ CH+

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: https://notendur.hi.is/agust/rannsoknir/papers/jpcA114-9991-10.pdf