2 color VMI exp CH 3X v 1

2 color VMI exp. CH 3(X; v 1 v 2 v 3 v 4) detection; https: //notendur. hi. is/~agust/rannsoknir/Crete 16/PPT-161116 -CH 3 Br(5). pptx Content: KERs for Ry(72977; 274. 14 nm), CH 3(211) detection…………………. . possible procedures…………………………………. . CH 3 Br absorption spectra and possible probe absorption……………. . Image and KER for Ry(72977; 274. 14 nm), CH 3(000) detection…. ………………. . Comparison with Theos work from 2009…………………. Vibrational frequencies: CH 3´s and CH 3 Br´s…………………………. CH 3 2 color KERS and possible explanation………………. . …………………. vibrational structure…………………………. comparison of peaks due to 1 hv excitation and CH 3(X) + Br/Br* formation……. . Udated: 180816 (slide 30) pages: 2, 4 -6 3 7 -9 12 -16 19 -28 29 30 10 -11 17 -18

KERs (xx) / CH 3(211; 329. 5 nm) detect. : i. e. : CH 3**(3 p, 2 A 2; 0100) CH 3 (X ; 0100) 2 -color; Both lasers Ry(2 hv/cm-1): 72977/274. 14 nm (10. 11. 16) Pump (Dye laser; 274. 14 nm; 72977(Ry)) Probe (MOPO; 329. 5 nm; CH 3(211) Could these be due to CH 3+ formed via CH 3 Br + 1 hv and/or 2 hv(274. 14) -> CH 3 + Br*/Br ? e. V https: //notendur. hi. is/~agust/rannsoknir/Crete 16/PXP-161116. pxp; Gr: 1, Lay: 0 https: //notendur. hi. is/~agust/rannsoknir/Crete 16/XLS-160912. xlsx; Waves.

To top i. e. : according to the 2 color processes: CH 3 r o col n: o Tw ctio e det c) CH 3+ + Br/Br* CH 3+ + Br/(Br*) c) 3 hv b) Ry(p) CH 3* + Br/(Br*) CH 3 **(3 p 2 A 2)+ Br/Br* pump KERs 2 hv Ry(s)? 2 hv a) 1 hv KERs 1 hv a-b) probe CH 3 + Br* CH 3 + Br See also https: //notendur. hi. is/~agust/rannsoknir/Crete 16/PPT-160921 -CH 3 Br(3). pptx slide 41

2 -color; Both lasers Ry(72977; 274. 14 nm); CH 3(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; CH 3(211) From Pavle, 10. 11. 2016

Absorption spectra for CH 3 Br 103 – 207 nm (~48400 – 96800 cm-1) cm-1 https: //notendur. hi. is/~agust/rannsoknir/Crete 16/Absorbance_spectra_CH 3 Br_vs_CH 3_res. pxp ; Gr: 2

5 s : [3/2]5 s 5 s’ : [1/2]5 s 5 s 5 s’ cm-1 2 hv energy for probe laser for (329. 5 nm)CH 3(X) - - - 1 hv absorption spectra Locht et. al. 2005 (see link) -------http: //satellite. mpic. de/spectral_atlas/cross_sections/Halogeno-alkanes+radicals/Bromoalkanes/CH 3 Br_Locht(2005)_298 K_103 -207 nm. txt https: //notendur. hi. is/~agust/rannsoknir/Crete 16/Absorbance_spectra_CH 3 Br_vs_CH 3_res. pxp ; Gr: 2

5 s’ 0 Close up of region where 2 hv probe laser reaches. Definitely some absorbance in this region for CH 3 Br n 2 n 3 cm-1 https: //notendur. hi. is/~agust/rannsoknir/Crete 16/Absorbance_spectra_CH 3 Br_vs_CH 3_res. pxp ; Gr: 2 Causley and Russel (1974)

Pavlé; e-mail 15. 11. 2016: : Initially we wanted to record ground state CH 3 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. 14 nm) 2 -color exp. CH 3 (000) detection NB: Worth getting a KER!

2 -color; Both lasers; Ry(72977; 274. 14 nm); CH 3(000; 333. 5 nm) detect. : i. e. : CH 3**(3 p, 2 A 2; 0000) CH 3 (X ; 0000) From Pavle, e-mail, 17. 11. 2016

https: //notendur. hi. is/~agust/rannsoknir/papers/jcp 130 -034304 -09. pdf; V. Blanchet et al. 2009 https: //notendur. hi. is/~agust/rannsoknir/papers/pccp 11 -2234 -09. pdf; Theo et al. , 2009 left arrow: 1 hv = 29976 cm-1; right arrow: 29069. 8 cm-1 # + + 2 # CH 3 + Br CH 3 Br **(B E) CH 3 Br+**(A 2 A 1) # Our Scanning range Ours # https: //notendur. hi. is/~agust/rannsoknir/Crete 16/XLS-160912. xlsx; “Energetics” https: //notendur. hi. is/~agust/rannsoknir/Crete 16/PXP-161130 -energetics-CH 3. pxp; Gr: 0; Lay: 0

2 hv for probe = 329. 5 nm (CH 3, 211 detection) Region scanned by Theo, 2009 *: * https: //notendur. hi. is/~agust/rannsoknir/papers/pccp 11 -2234 -09. pdf https: //notendur. hi. is/~agust/rannsoknir/Crete 16/XLS-160912. xlsx; “various things” https: //notendur. hi. is/~agust/rannsoknir/Crete 16/Absorbance_spectra_CH 3 Br_vs_CH 3_res. pxp ; Gr: 2, Lay: 0 Standard Absorption spectrum cm-1

CH 3; KERs /, pump = 274. 14; probe = 329. 5 nm (CH 3, 211 detection) and comparison with Theos work from 2016: Max thresholds for our data as indicated pump probe 2 colors probe # CH 3 Br+(E 1/2) + 1 hv CH 3++Br/Br* CH 3 Br+(E 3/2) + 1 hv CH 3++Br/Br* CH 3 Br + 1 hv CH 3+Br/Br* Ry(2 hv/cm-1): 72977/274. 14 pump (10. 11. 16) Br Br* 29976. 0 cm-1 333. 6 nm https: //notendur. hi. is/~agust/rannsoknir/papers/pccp 11 -2234 -09. pdf; Theo et al. , 2009; One-color CH 3+ KERS, 29940. 1 cm-1 334. 0 nm Probe (MOPO) KER(CH 3) / e. V* https: //notendur. hi. is/~agust/rannsoknir/Crete 16/CH 3 Br-crete 2016 -161130 AH. xlsx ; sheet: “ 60698 “(for thresholds) https: //notendur. hi. is/~agust/rannsoknir/Crete 16/Two_colour_CH 3 -161128 AH. pxp; Lay: 0; Gr: 1 https: //notendur. hi. is/~agust/rannsoknir/Crete 16/XLS-171001 -CH 3 Br. xlsx; sheet: Predictions-s # *f= 2. 98 x 10 -5

Interpretations of spectral features: # KER(CH 3) / e. V* # Most probably he is accidentally on resonance for CH 3(X) 000 and detecting CH 3(X, 0000) formed by 1 hv + CH 3 Br -> CH 3(X, 0000) + Br (180810) *f= 2. 98 x 10 -5 https: //notendur. hi. is/~agust/rannsoknir/Crete 16/Two_colour_CH 3 -161128 AH. pxp; Lay: 0; Gr: 1 https: //notendur. hi. is/~agust/rannsoknir/papers/pccp 11 -2234 -09. pdf; Theo et al. , 2009; One-color CH 3+ KERS,

https: //notendur. hi. is/~agust/rannsoknir/papers/pccp 11 -2234 -09. pdf; Theo et al. , 2009; One-color CH 3+ KERS, https: //notendur. hi. is/~agust/rannsoknir/Crete 16/Electron_KER-161201 AH. pxp ; Gr: 0 (left); Gr: 13 (right)

OPLAs: CH 3+ CH 3**3 p 2 A 2 CH 3(X) T S I N

CH 3 Br+(X) T S NI CH 3 Br(X)

Pump (dye l. ): 255. 317 nm/ 78334 cm-1/(9 a) Probe(mopo): 333. 488 nm Probe(mopo): 333. 900 nm 1 11 0 00 e. V Probe(mopo): 329. 500 nm Probe(mopo): 325. 800 nm 2 22 2 11 e. V https: //notendur. hi. is/agust/rannsoknir/Crete 17/PXP-171128. pxp ; Lay 0, Gr: 1, 4, 5, 3

Pump (dye l. ): 251. 24 nm/ 79620 cm-1/(10): Pump (dye l. ): 274. 14 nm/ 72977 cm-1/(5): Probe(mopo): 329. 500 nm Probe(mopo): 333. 488 nm 0 2 11 00 e. V Ry(2 hv/cm-1): 72977/274. 14 pump (10. 11. 16) Ry(2 hv/cm-1): 79620/251. 24 pump (29. 05. 17) https: //notendur. hi. is/~agust/rannsoknir/Crete 16/XLS-160912. xlsx; Sheet: Waves. https: //notendur. hi. is/agust/rannsoknir/Crete 17/PXP-171128. pxp ; Lay 2, Gr: 2 https: //notendur. hi. is/agust/rannsoknir/Crete 17/PXP-171128. pxp ; Lay 1, Gr: 7

Region scanned by Theo, 2009 *: 5 s’ 5 s Standard Absorption spectrum 0 2 hv for probeing of CH 3(X): 111 000 n 3 * https: //notendur. hi. is/~agust/rannsoknir/papers/pccp 11 -2234 -09. pdf https: //notendur. hi. is/~agust/rannsoknir/Crete 16/XLS-160912. xlsx; Sheets: “various things” & “Waves” https: //notendur. hi. is/~agust/rannsoknir/Crete 16/Absorbance_spectra_CH 3 Br_vs_CH 3_res. pxp ; Gr: 2, Lay: 0 211 222 n 2 cm-1

Explanation idea(? ) : To top H 3 r C o l o c Two ction: e det CH 3++Br/(Br*) CH 3+ + Br/Br* CH 3+ + Br/Br* 3 hvr, pd CH 3 Br+ (X, 3/2, 1/2) CH 3 **+ Br/Br* CH 3 **(3 p 2 A 2)+ Br/Br* Ry(p) pump Ry(s) Probe CH 3(X; v 1 v 2 v 3 v 4) probe transitions 1 hvpd (10) (no. 5) (9) KERs 1 hv v´ i v´´ CH 3 + Br* CH 3 + Br See also https: //notendur. hi. is/~agust/rannsoknir/Crete 16/PPT-160921 -CH 3 Br(3). pptx slide 41

Excitation and energetic scheme for 2 color MPI, in scale / alternative idea 2: CH 3+ + CH 3+ CH CH 3+ 3 + CH 3+ + Br/Br* cm-1 CH 3 Br+ (X, 3/2, 1/2) CH 3 **(3 p 2 A 2)+ Br/Br* Pump(no 9; 2 hv=78370) Probe CH 3(211) 2 hv= 60698 KERs 1 hv CH 3 + Br* CH 3 + Br r/A https: //notendur. hi. is/agust/rannsoknir/Crete 17/PXP-171130. pxp ; Lay 0, Gr 0

s on R E K f o rison a p m ale o c c s ) H *f(C 3 a (1 hv) E(Br*)-E(Br) CH 3(X; v 1 v 2 v 3 v 4) + Br* CH 3(X; v 1 v 2 v 3 v 4) + Br Z component D(1 hv)*f(CH 3) https: //notendur. hi. is/agust/rannsoknir/Crete 17/PXP-171128. pxp ; Lay 3, Gr: 8

After „cleaning“ of spikes by Pavle (send by messanger 171129): „Normalized“ preferred agust, heima, …. rannsóknir/Crete-17/CH 3 Br/….

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 CH 3(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 CH 3 Br_502. 480 DIV 2_CH 3_000 I have just sent you another email, with the correct KER of CH 3(000) at 251. 140 nm Files were transfered to agust, heima, . . rannsoknir/Crete-17/CH 3 Br/CH 3 -two-color/…

s on R E K f ison o ale; r a p m co sc H C 3) ( f * ) a (1 hv ctra e p s d cleane E(Br*)-E(Br) CH 3(X; v 1 v 2 v 3 v 4) + Br* CH 3(X; v 1 v 2 v 3 v 4) + Br Z component D(1 hv)*f(CH 3) / e. V https: //notendur. hi. is/agust/rannsoknir/Crete 17/PXP-171128. pxp ; Lay 4, 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. 98 e-5) too high).

g n o r , w ation O N et 16) r p 8 r inte y: 180 tr (en From pavle/messenger 171201

CH 3 KERs: One color (old), 2 hv = 79610 cm-1 a) One color (new), 2 hv = 79610 cm-1 a) Two-color (pump + probe(000 detection)); 2 hv = 79610 cm-1 One-color (old), 2 hv = 77165 cm-1 a) Different conditions, Possibly(? ): new colder than old *f= 2. 98 x 10 -5