2 color VMI exp. CH3(X;v1v2v3v4) detection; https://notendur. hi Content: pages: KERs for Ry(72977; 274.14nm), CH3(211) detection…………………. ……………….. 2,4-6 possible procedures………………………………………………………………….. ……………….. 3 CH3Br absorption spectra and possible probe absorption………………………….. 7-9 Image and KER for Ry(72977; 274.14nm), CH3(000) detection…. ……………….. 10-11 Comparison with Theos work from 2009………………………………….. …………………. 12-16 Vibrational frequencies: CH3´s and CH3Br´s…………………………………………………. 17-18 CH3 2 color KERS and possible explanation……………………………….. …………………. 19-28 vibrational structure………………………………… ……………………………………………………. 29 comparison of peaks due to 1hv excitation and CH3(X) + Br/Br* formation…….. 30 Udated: 180816 (slide 30)

Could these be due to CH3+ formed via CH3Br + 1hv and/or 2hv(274.14) KERs (xx) / CH3(211; 329.5 nm) detect.: i.e.: CH3**(3p,2A2;0100) CH3 (X ;0100) 2-color; Both lasers Ry(2hv/cm-1): 72977/274.14 nm (10.11.16) Pump (Dye laser; 274.14 nm; 72977(Ry)) Probe (MOPO; 329.5 nm; CH3(211) Could these be due to CH3+ formed via CH3Br + 1hv and/or 2hv(274.14) -> CH3 + Br*/Br ? eV https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; Waves.  https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-161116.pxp; Gr:1, Lay:0

i.e. : according to the 2 color processes: To top i.e. : according to the 2 color processes: Two color CH3 detection: c) CH3+ + Br/Br* CH3+ + Br/(Br*) c) 3hv CH3* + Br/(Br*) pump CH3 **(3p2A2)+ Br/Br* b) Ry(p) Ry(s)? KERs 2hv a-b) probe 2hv a) KERs 1hv CH3 + Br* 1hv CH3 + Br See also https://notendur.hi.is/~agust/rannsoknir/Crete16/PPT-160921-CH3Br(3).pptx slide 41

2-color; Both lasers Ry(72977; 274.14nm); CH3(211; 329.5 nm) detect.: ? Do not understand From Pavle, 10.11.2016

Pump (Dye laser; 274.14 nm; 72977(Ry)) From Pavle, 10.11.2016

Probe (MOPO; 329.5 nm; CH3(211) From Pavle, 10.11.2016

Absorption spectra for CH3Br 103 – 207nm (~48400 – 96800 cm-1) https://notendur.hi.is/~agust/rannsoknir/Crete16/Absorbance_spectra_CH3Br_vs_CH3_res.pxp ; Gr:2

2hv energy for probe laser for (329.5nm)CH3(X) - - - - 5s : [3/2]5s 5s’ : [1/2]5s 5s’ 5s cm-1 2hv energy for probe laser for (329.5nm)CH3(X) - - - - 1 hv absorption spectra Locht et.al. 2005 (see link) -------- http://satellite.mpic.de/spectral_atlas/cross_sections/Halogeno-alkanes+radicals/Bromoalkanes/CH3Br_Locht(2005)_298K_103-207nm.txt https://notendur.hi.is/~agust/rannsoknir/Crete16/Absorbance_spectra_CH3Br_vs_CH3_res.pxp ; Gr:2

Close up of region where 2 hv probe laser reaches. Close up of region where 2 hv probe laser reaches. Definitely some absorbance in this region for CH3Br n2 n3 cm-1 Causley and Russel (1974) https://notendur.hi.is/~agust/rannsoknir/Crete16/Absorbance_spectra_CH3Br_vs_CH3_res.pxp ; Gr:2

Pavlé; e-mail 15.11.2016: : Initially we wanted to record ground state CH3 through 000 vibronic transition at around 333.5 nm, but the power of the laser at 333.5 was a bit low. We recorded only one image and decided to leave this for later. You can see the image in the first attachment, it shows some rings. : Ry(72977; 274.14nm) 2-color exp. CH3 (000) detection NB: Worth getting a KER!

2-color; Both lasers; Ry(72977; 274.14nm); CH3(000; 333.5 nm) detect.: i.e.: CH3**(3p,2A2;0000) CH3 (X ;0000) From Pavle, e-mail, 17.11.2016

Ours CH3Br+**(B2E) CH3 + Br+ CH3Br+**(A2A1) Our Scanning range https://notendur.hi.is/~agust/rannsoknir/papers/jcp130-034304-09.pdf; V. Blanchet et al. 2009 https://notendur.hi.is/~agust/rannsoknir/papers/pccp11-2234-09.pdf; Theo et al., 2009 left arrow: 1hv = 29976 cm-1; right arrow: 29069.8 cm-1 CH3Br+**(B2E) # CH3 + Br+ # CH3Br+**(A2A1) # Our Scanning range Ours # https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; “Energetics” https://notendur.hi.is/~agust/rannsoknir/Crete16/PXP-161130-energetics-CH3.pxp; Gr:0; Lay:0

2hv for probe = 329.5 nm (CH3,211detection) Standard Region scanned by Absorption spectrum Region scanned by Theo, 2009 *: cm-1 * https://notendur.hi.is/~agust/rannsoknir/papers/pccp11-2234-09.pdf https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; “various things” https://notendur.hi.is/~agust/rannsoknir/Crete16/Absorbance_spectra_CH3Br_vs_CH3_res.pxp ; Gr:2, Lay:0

Max thresholds for our data as indicated CH3; KERs /,pump = 274.14; probe = 329.5 nm (CH3,211detection) and comparison with Theos work from 2016: Max thresholds for our data as indicated # 2 colors CH3Br+(E1/2) + 1hv CH3++Br/Br* Ry(2hv/cm-1): 72977/274.14 pump (10.11.16) probe pump probe pump CH3Br+(E3/2) + 1hv CH3++Br/Br* Br probe pump CH3Br + 1hv CH3+Br/Br* Br* 29976.0 cm-1 333.6 nm https://notendur.hi.is/~agust/rannsoknir/papers/pccp11-2234-09.pdf; Theo et al., 2009; One-color CH3+ KERS, 29940.1 cm-1 334.0 nm Probe (MOPO) KER(CH3) / eV* # https://notendur.hi.is/~agust/rannsoknir/Crete16/CH3Br-crete2016-161130AH.xlsx ; sheet: “60698 “(for thresholds) https://notendur.hi.is/~agust/rannsoknir/Crete16/Two_colour_CH3-161128AH.pxp; Lay:0; Gr:1 https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-171001-CH3Br.xlsx; sheet: Predictions-s *f= 2.98x10-5

Interpretations of spectral features: # KER(CH3) / eV* # Most probably he is accidentally on resonance for CH3(X) 000 and detecting CH3(X,0000) formed by 1hv + CH3Br -> CH3(X,0000) + Br (180810) *f= 2.98x10-5 https://notendur.hi.is/~agust/rannsoknir/papers/pccp11-2234-09.pdf; Theo et al., 2009; One-color CH3+ KERS, https://notendur.hi.is/~agust/rannsoknir/Crete16/Two_colour_CH3-161128AH.pxp; Lay:0; Gr:1

https://notendur. hi. is/~agust/rannsoknir/papers/pccp11-2234-09 https://notendur.hi.is/~agust/rannsoknir/papers/pccp11-2234-09.pdf; Theo et al., 2009; One-color CH3+ KERS, https://notendur.hi.is/~agust/rannsoknir/Crete16/Electron_KER-161201AH.pxp ;Gr:0 (left); Gr:13 (right)

OPLAs: CH3+ CH3**3p2A2 CH3(X) NIST

CH3Br+(X) CH3Br(X) NIST

1 2 2 Pump (dye l.): 255.317 nm/ 78334 cm-1/(9a) 1 1 eV 2 1 2 1 eV Probe(mopo): 333.488 nm Probe(mopo): 333.900 nm 1 1 1 eV Probe(mopo): 329.500 nm Probe(mopo): 325.800 nm 2 1 2 2 2 1 eV https://notendur.hi.is/agust/rannsoknir/Crete17/PXP-171128.pxp ; Lay0, Gr:1,4,5,3

2 1 1 eV Pump (dye l.): 274.14 nm/ 72977 cm-1/(5): Probe(mopo): 329.500 nm Probe(mopo): 333.488 nm 1 2 1 eV Ry(2hv/cm-1): 72977/274.14 pump (10.11.16) Ry(2hv/cm-1): 79620/251.24 pump (29.05.17) https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; Sheet: Waves.  https://notendur.hi.is/agust/rannsoknir/Crete17/PXP-171128.pxp ; Lay1, Gr:7 https://notendur.hi.is/agust/rannsoknir/Crete17/PXP-171128.pxp ; Lay2, Gr:2

1 2 2 Region scanned by Theo, 2009 *: 2hv for probeing of CH3(X): 5s’ 2 1 2 Standard Absorption spectrum n3 n2 cm-1 * https://notendur.hi.is/~agust/rannsoknir/papers/pccp11-2234-09.pdf https://notendur.hi.is/~agust/rannsoknir/Crete16/XLS-160912.xlsx; Sheets: “various things” & “Waves” https://notendur.hi.is/~agust/rannsoknir/Crete16/Absorbance_spectra_CH3Br_vs_CH3_res.pxp ; Gr:2, Lay:0

Two color CH3 detection: Explanation idea(?) : To top Two color CH3 detection: CH3+ + Br/Br* CH3++Br/(Br*) CH3+ + Br/Br* 3hvr,pd CH3Br+ (X,3/2,1/2) CH3 **+ Br/Br* Ry(p) CH3 **(3p2A2)+ Br/Br* pump Ry(s) Probe CH3(X;v1v2v3v4) probe i v´ v´´ transitions 1hvpd KERs 1hv CH3 + Br* (no. 5) (10) CH3 + Br (9) See also https://notendur.hi.is/~agust/rannsoknir/Crete16/PPT-160921-CH3Br(3).pptx slide 41

cm-1 r/A CH3+ CH3+ CH3+ + Br/Br* CH3+ CH3+ + Pump(no 9; 2hv=78370) Excitation and energetic scheme for 2 color MPI, in scale / alternative idea 2: CH3+ CH3+ CH3+ + Br/Br* CH3+ CH3+ CH3+ + Br/Br* cm-1 CH3Br+ (X,3/2,1/2) CH3 **(3p2A2)+ Br/Br* Pump(no 9; 2hv=78370) Probe CH3(211) 2hv= 60698 KERs 1hv CH3 + Br* CH3 + Br r/A https://notendur.hi.is/agust/rannsoknir/Crete17/PXP-171130.pxp ; Lay0, Gr0

comparison of KERs on a (1hv)*f(CH3) scale E(Br*)-E(Br) D(1hv)*f(CH3) CH3(X;v1v2v3v4) + Br* CH3(X;v1v2v3v4) + Br Z component D(1hv)*f(CH3) https://notendur.hi.is/agust/rannsoknir/Crete17/PXP-171128.pxp ; Lay3, Gr:8

After „cleaning“ of spikes by Pavle (send by messanger 171129): „Normalized“ preferred agust,heima,….rannsóknir/Crete/Crete-17/CH3Br/….

Messenger, wed (171129): So, finally I have sent you the Origin graphs 5 origin files, because the sixth one (dissociation at 274 nm and probing of CH3(211) was okay And the Excel file, with the summary of the experiments just a second, I noticed that I sent you an older version of CH3Br_502.480DIV2_CH3_000 I have just sent you another email, with the correct KER of CH3(000) at 251.140 nm Files were transfered to agust,heima,..rannsoknir/Crete/Crete-17/CH3Br/CH3-two-color/…

comparison of KERs on a (1hv)*f(CH3) scale; E(Br*)-E(Br) cleaned spectra E(Br*)-E(Br) CH3(X;v1v2v3v4) + Br* CH3(X;v1v2v3v4) + Br Z component D(1hv)*f(CH3) / eV https://notendur.hi.is/agust/rannsoknir/Crete17/PXP-171128.pxp ; Lay4, Gr:9

Spacing between „sharp“ peaks in the KERs is close to E(Br*)-E(Br) Reasonably good fit for Ry peak no. 10 (000 probing) vs. both „sharp“ peaks Relative intensity of the „sharp“ non-resonance paeks vs. broad feature peaking at low KER increases as (5) < (9) <(10) as to be expected. Measures peaks tend to appear at higher KER values than predicted (analogous is found for Br+ two color „sharp“peak) (Is the pixel factor 2.98e-5) too high).

NO, wrong interpretation (entry: 180816) From pavle/messenger 171201

CH3 KERs: One color (old), 2hv = 79610 cm-1 a) One color (new), 2hv = 79610 cm-1 a) Two-color (pump + probe(000 detection)); 2hv = 79610 cm-1 2hv = 79610 cm-1 One-color (old), 2hv = 77165 cm-1 Different conditions, Possibly(?): new colder than old *f= 2.98x10-5