1. HBr, (updated 101213; slide 12) V(m+i) /HBr+(v+) spectra analysis https://notendur.hi.is/~agust/rannsoknir/Crete/PPT-131206.pptx

2. https://notendur.hi.is/~agust/rannsoknir/Crete/PXP-131206.pxp HBr, V(m+5), J´=0, Gaussian fits to HBr + (v + ) peaks

3. BaselineType: Constant y0 = 0.03 +/- 0 Peak 0Type: Gauss Location = 1.6254 +/- 0.0018921 Height = 0.12362 +/- 0.0072314 Area = 0.0086841 +/- 0.00050824 FWHM = 0.065993 +/- 0.0044679 Fit function parameters Location =1.6254+/-0.0018921 Width =0.039633+/-0.0026833 Height =0.12362+/-0.0072314 Peak 1Type: Gauss Location = 1.8112 +/- 0.0010983 Height = 0.24415 +/- 0.0066662 Area = 0.021318 +/- 0.00058294 FWHM = 0.082029 +/- 0.0025972 Fit function parameters Location =1.8112+/-0.0010983 Width =0.049263+/-0.0015598 Height =0.24415+/-0.0066662 Peak 2Type: Gauss Location = 1.9863 +/- 0.00054468 Height = 0.49805 +/- 0.0068995 Area = 0.042509 +/- 0.00058974 FWHM = 0.080182 +/- 0.0012878 Fit function parameters Location =1.9863+/-0.00054468 Width =0.048154+/-0.00077342 Height =0.49805+/-0.0068995 Fit completed 12:45 6. desember 2013 Y data wave: root:wave11[275, 322] X data wave: root:wave10 Chi square: 0.0058548 Total fitted points: 48 Multi-peak fit version 2.00 https://notendur.hi.is/~agust/rannsoknir/Crete/PXP-131206.pxp

4. HBr, V(m+5) https://notendur.hi.is/~agust/rannsoknir/Crete/PXP-131206.pxphttps://notendur.hi.is/~agust/rannsoknir/Crete/PXP-131206.pxp; Gr3, Lay3 HBr, V(m+5), J´= 0, Gaussian fits to HBr + (v + ) and HBr + * (v + ) peaks

5. BaselineType: Constant y0 = 0.03 +/- 0 Peak 0Type: Gauss Location = 1.4912 +/- 0.0013104 Height = 0.14398 +/- 0.0063173 Area = 0.0093315 +/- 0.00041027 FWHM = 0.060885 +/- 0.0031006 Fit function parameters Location =1.4912+/-0.0013104 Width =0.036565+/-0.0018621 Height =0.14398+/-0.0063173 Peak 1Type: Gauss Location = 1.6255 +/- 0.0016053 Height = 0.12423 +/- 0.0062398 Area = 0.0086194 +/- 0.00043374 FWHM = 0.065182 +/- 0.0038007 Fit function parameters Location =1.6255+/-0.0016053 Width =0.039146+/-0.0022826 Height =0.12423+/-0.0062398 Peak 2Type: Gauss Location = 1.8112 +/- 0.00094142 Height = 0.24412 +/- 0.0057123 Area = 0.021321 +/- 0.00049963 FWHM = 0.082046 +/- 0.0022262 Fit function parameters Location =1.8112+/-0.00094142 Width =0.049274+/-0.001337 Height =0.24412+/-0.0057123 Peak 3Type: Gauss Location = 1.9863 +/- 0.00046678 Height = 0.49805 +/- 0.0059129 Area = 0.042508 +/- 0.0005054 FWHM = 0.08018 +/- 0.0011037 Fit function parameters Location =1.9863+/-0.00046678 Width =0.048153+/-0.00066281 Height =0.49805+/-0.0059129 Fit completed 13:12 6. desember 2013 Y data wave: root:wave11[257, 321] X data wave: root:wave10 Chi square: 0.0058436 Total fitted points: 65 Multi-peak fit version 2.00 https://notendur.hi.is/~agust/rannsoknir/Crete/PXP-131206.pxp

6. Peaks can easily be fitted by Gaussian functions. ERGO: It is a good approximation to assume individual peaks to represent Ionization of one J + (i.e. J + = 0) level (and not e.g. (thermal) rotational distribution) This makes sence, since the transition involves: 1)Q line, J‘‘ = J‘ = 0 two-photon resonance transition followed by 2)J´= 0 to J + transition(s) -and in the latter case (2) the most probable transition is likely to be the J´= 0 -> J + = 0 transition (see for example https://notendur.hi.is/~agust/rannsoknir/papers/jcp97-2891-92.pdf ) https://notendur.hi.is/~agust/rannsoknir/papers/jcp97-2891-92.pdf

7. HBr, E(0), J´= 1, Gaussian fits to HBr + (v + ) and HBr + * (v + ) peaks https://notendur.hi.is/~agust/rannsoknir/Crete/PXP-131207.pxphttps://notendur.hi.is/~agust/rannsoknir/Crete/PXP-131207.pxp, Gr:4,Lay3

8. BaselineType: Constant y0 = 0.018768 +/- 0.0015388 Peak 0Type: Gauss Location = 1.2936 +/- 0.0031788 Height = 0.024038 +/- 0.0025784 Area = 0.0017106 +/- 0.00027058 FWHM = 0.066854 +/- 0.0090887 Fit function parameters Location =1.2936+/-0.0031788 Width =0.04015+/-0.0054583 Height =0.024038+/-0.0025784 Peak 1Type: Gauss Location = 1.4682 +/- 0.0031111 Height = 0.106 +/- 0.0035818 Area = 0.012393 +/- 0.00089374 FWHM = 0.10984 +/- 0.0052706 Fit function parameters Location =1.4682+/-0.0031111 Width =0.065963+/-0.0031653 Height =0.106+/-0.0035818 Peak 2Type: Gauss Location = 1.5936 +/- 0.0047969 Height = 0.066292 +/- 0.0025593 Area = 0.0085986 +/- 0.0010523 FWHM = 0.12185 +/- 0.013002 Fit function parameters Location =1.5936+/-0.0047969 Width =0.073179+/-0.0078085 Height =0.066292+/-0.0025593 Peak 3Type: Gauss Location = 1.7875 +/- 0.0018818 Height = 0.12223 +/- 0.0022788 Area = 0.019086 +/- 0.00081219 FWHM = 0.14668 +/- 0.0066127 Fit function parameters Location =1.7875+/-0.0018818 Width =0.088093+/-0.0039713 Height =0.12223+/-0.0022788 Peak 4Type: Gauss Location = 1.957 +/- 0.0012576 Height = 0.19446 +/- 0.0024252 Area = 0.026884 +/- 0.0007338 FWHM = 0.12988 +/- 0.0028025 Fit function parameters Location =1.957+/-0.0012576 Width =0.077998+/-0.0016831 Height =0.19446+/-0.0024252 Fit completed 16:02 7. desember 2013 Y data wave: root:wave1[240, 322] X data wave: root:wave0 Chi square: 0.0011427 Total fitted points: 83 Multi-peak fit version 2.00 HBr, E(0), J´= 1, Gaussian fits to HBr + (v + ) and HBr + * (v + ) peaks https://notendur.hi.is/~agust/rannsoknir/Crete/PXP-131207.pxphttps://notendur.hi.is/~agust/rannsoknir/Crete/PXP-131207.pxp, Gr:4,Lay3

9. HBr, E(0), J´=1 BaselineType: Constant y0 = 0.018768 +/- 0.0015388 Peak 0FWHM = 0.066854 +/- 0.0090887 Peak 1FWHM = 0.10984 +/- 0.0052706 Peak 2FWHM = 0.12185 +/- 0.013002 Peak 3FWHM = 0.14668 +/- 0.0066127 Peak 4FWHM = 0.12988 +/- 0.0028025 HBr, V(m+5), J´= 0 BaselineType: Constant y0 = 0.03 +/- 0 Peak 0FWHM = 0.060885 +/- 0.0031006 Peak 1FWHM = 0.065182 +/- 0.0038007 Peak 2FWHM = 0.082046 +/- 0.0022262 Peak 3FWHM = 0.08018 +/- 0.0011037 Summary:

10.  Linewidths are larger for E(0) than V(m+5) (and V(m+i) in general!)  This suggests that lifetime(s)(?) are shorter for E(0) in general! At first sight this seems to contradicts(?) with the linewidth date for the REMPI spectra ( https://notendur.hi.is/~agust/rannsoknir/papers/jcp138-044308-13. pdf ): https://notendur.hi.is/~agust/rannsoknir/papers/jcp138-044308-13. pdf which suggest that Linewidths of the V(m+5) (and V(m+4)) are generally larger (see next slide) (Actually this does not hold for V(m+5), J´= 0, however!!) Judging from the KER spectra for V(m+4) (see PPT-131111.ppt/ https://notendur.hi.is/~agust/rannsoknir/Crete/PPT-131111.pptx ) https://notendur.hi.is/~agust/rannsoknir/Crete/PPT-131111.pptx E(0) (see HBr-E0-KER-131106.ppt/ https://notendur.hi.is/~agust/rannsoknir/Crete/HBr-E0-KER-131106.pptx ) https://notendur.hi.is/~agust/rannsoknir/Crete/HBr-E0-KER-131106.pptx V(m+5) (see PPT-131112.ppt/ https://notendur.hi.is/~agust/rannsoknir/Crete/PPT-131112.pptx ) https://notendur.hi.is/~agust/rannsoknir/Crete/PPT-131112.pptx It seems as if linewidths of the V(m+5) (and V(m+4)) are smaller than for E(0), hence That lifetimes of the V(m+5) (and V(m+4)) are larger than for E(0)! BUT are we talking about lifetimes of the E(0) and V(m+i) states or broadening associated with different ionization processes?

11. https://notendur.hi.is/~agust/rannsoknir/papers/jcp138-044308-13.pdf

12. Possible explanation(?): RyV/Ion-pair H + + Br (3/2)/Br*(1/2) Dominant E(0) transition involves more autoionization, i.e. transition to a superexcited state/ repulsive state an dissociation (to form H + Br**) to lower effective lifetime of HBr+(?) Dominant V(m+i) transition involves less autoionization/ more direct ionization/HBr+ formation H + Br**(5s)