HBr, (updated 101213; slide 12)

V(m+i) /HBr+(v+) spectra analysis

https://notendur.hi.is/~agust/rannsoknir/Crete/PPT-131206.pptx

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https://notendur.hi.is/~agust/rannsoknir/Crete/PXP-131206.pxp

HBr, V(m+5), J´=0, Gaussian fits to HBr+ (v+) peaks

Baseline Type: Constant

y0 = 0.03 +/- 0

Peak 0 Type: Gauss

Location = 1.6254 +/- 0.0018921Height = 0.12362 +/- 0.0072314Area = 0.0086841 +/- 0.00050824FWHM = 0.065993 +/- 0.0044679

Fit function parametersLocation = 1.6254 +/- 0.0018921Width = 0.039633 +/- 0.0026833Height = 0.12362 +/- 0.0072314

Peak 1 Type: Gauss

Location = 1.8112 +/- 0.0010983Height = 0.24415 +/- 0.0066662Area = 0.021318 +/- 0.00058294FWHM = 0.082029 +/- 0.0025972

Fit function parametersLocation = 1.8112 +/- 0.0010983Width = 0.049263 +/- 0.0015598Height = 0.24415 +/- 0.0066662

Peak 2 Type: Gauss

Location = 1.9863 +/- 0.00054468Height = 0.49805 +/- 0.0068995Area = 0.042509 +/- 0.00058974FWHM = 0.080182 +/- 0.0012878

Fit function parametersLocation = 1.9863 +/- 0.00054468Width = 0.048154 +/- 0.00077342Height = 0.49805 +/- 0.0068995

Fit completed 12:45 6. desember 2013Y data wave: root:wave11[275, 322]X data wave: root:wave10Chi square: 0.0058548Total fitted points: 48Multi-peak fit version 2.00

https://notendur.hi.is/~agust/rannsoknir/Crete/PXP-131206.pxp

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HBr, V(m+5)

https://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

Baseline Type: Constant

y0 = 0.03 +/- 0

Peak 0 Type: Gauss

Location = 1.4912 +/- 0.0013104Height = 0.14398 +/- 0.0063173Area = 0.0093315 +/- 0.00041027FWHM = 0.060885 +/- 0.0031006

Fit function parametersLocation = 1.4912 +/- 0.0013104Width = 0.036565 +/- 0.0018621Height = 0.14398 +/- 0.0063173

Peak 1 Type: Gauss

Location = 1.6255 +/- 0.0016053Height = 0.12423 +/- 0.0062398Area = 0.0086194 +/- 0.00043374FWHM = 0.065182 +/- 0.0038007

Fit function parametersLocation = 1.6255 +/- 0.0016053Width = 0.039146 +/- 0.0022826Height = 0.12423 +/- 0.0062398

Peak 2 Type: Gauss

Location = 1.8112 +/- 0.00094142Height = 0.24412 +/- 0.0057123Area = 0.021321 +/- 0.00049963FWHM = 0.082046 +/- 0.0022262

Fit function parametersLocation = 1.8112 +/- 0.00094142Width = 0.049274 +/- 0.001337Height = 0.24412 +/- 0.0057123

Peak 3 Type: Gauss

Location = 1.9863 +/- 0.00046678Height = 0.49805 +/- 0.0059129Area = 0.042508 +/- 0.0005054FWHM = 0.08018 +/- 0.0011037

Fit function parametersLocation = 1.9863 +/- 0.00046678Width = 0.048153 +/- 0.00066281Height = 0.49805 +/- 0.0059129

Fit completed 13:12 6. desember 2013Y data wave: root:wave11[257, 321]X data wave: root:wave10Chi square: 0.0058436Total fitted points: 65Multi-peak fit version 2.00

https://notendur.hi.is/~agust/rannsoknir/Crete/PXP-131206.pxp

Peaks can easily be fitted by Gaussian functions.ERGO: It is a good approximation to assume individual peaks to representIonization 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 by2) J´= 0 to J+ transition(s)-and in the latter case (2) the most probable transition is likely to be theJ´= 0 -> J+ = 0 transition (see for example https://notendur.hi.is/~agust/rannsoknir/papers/jcp97-2891-92.pdf)

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HBr, E(0), J´= 1, Gaussian fits to HBr+ (v+) and HBr+ *(v+) peaks

https://notendur.hi.is/~agust/rannsoknir/Crete/PXP-131207.pxp, Gr:4,Lay3

Baseline Type: Constant

y0 = 0.018768 +/- 0.0015388

Peak 0 Type: Gauss

Location = 1.2936 +/- 0.0031788Height = 0.024038 +/- 0.0025784Area = 0.0017106 +/- 0.00027058FWHM = 0.066854 +/- 0.0090887

Fit function parametersLocation = 1.2936 +/- 0.0031788Width = 0.04015 +/- 0.0054583Height = 0.024038 +/- 0.0025784

Peak 1 Type: Gauss

Location = 1.4682 +/- 0.0031111Height = 0.106 +/- 0.0035818Area = 0.012393 +/- 0.00089374FWHM = 0.10984 +/- 0.0052706

Fit function parametersLocation = 1.4682 +/- 0.0031111Width = 0.065963 +/- 0.0031653Height = 0.106 +/- 0.0035818

Peak 2 Type: Gauss

Location = 1.5936 +/- 0.0047969Height = 0.066292 +/- 0.0025593Area = 0.0085986 +/- 0.0010523FWHM = 0.12185 +/- 0.013002

Fit function parametersLocation = 1.5936 +/- 0.0047969Width = 0.073179 +/- 0.0078085Height = 0.066292 +/- 0.0025593

Peak 3 Type: Gauss

Location = 1.7875 +/- 0.0018818Height = 0.12223 +/- 0.0022788Area = 0.019086 +/-

0.00081219FWHM = 0.14668 +/- 0.0066127

Fit function parametersLocation = 1.7875 +/- 0.0018818Width = 0.088093 +/- 0.0039713Height = 0.12223 +/- 0.0022788

Peak 4 Type: Gauss

Location = 1.957 +/- 0.0012576Height = 0.19446 +/- 0.0024252Area = 0.026884 +/- 0.0007338FWHM = 0.12988 +/- 0.0028025

Fit function parametersLocation = 1.957 +/- 0.0012576Width = 0.077998 +/- 0.0016831Height = 0.19446 +/- 0.0024252

Fit completed 16:02 7. desember 2013Y data wave: root:wave1[240, 322]X data wave: root:wave0Chi square: 0.0011427Total fitted points: 83Multi-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.pxp, Gr:4,Lay3

HBr, E(0), J´=1

Baseline Type: Constant

y0 = 0.018768 +/- 0.0015388

Peak 0 FWHM = 0.066854 +/- 0.0090887

Peak 1 FWHM = 0.10984 +/- 0.0052706

Peak 2 FWHM = 0.12185 +/- 0.013002

Peak 3 FWHM = 0.14668 +/- 0.0066127

Peak 4 FWHM = 0.12988 +/- 0.0028025

HBr, V(m+5), J´= 0

Baseline Type: Constant

y0 = 0.03 +/- 0

Peak 0 FWHM = 0.060885 +/- 0.0031006

Peak 1 FWHM = 0.065182 +/- 0.0038007

Peak 2 FWHM = 0.082046 +/- 0.0022262

Peak 3 FWHM = 0.08018 +/- 0.0011037

Summary:

Þ Linewidths are larger for E(0) than V(m+5) (and V(m+i) in general!)Þ This suggests that lifetime(s)(?) are shorter for E(0) in general!

At first sight this seems to contradicts(?) with the linewidthdate for the REMPI spectra (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)E(0) (see HBr-E0-KER-131106.ppt/ 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)It seems as if linewidths of the V(m+5) (and V(m+4)) are smaller than for E(0), henceThat 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?

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

Possible explanation(?):

Ry V/Ion-pair

H+ + Br (3/2)/Br*(1/2)

Dominant E(0) transitioninvolves more autoionization,i.e. transition to a superexcited state/repulsive statean dissociation(to form H + Br**)to lower effectivelifetime of HBr+(?)

DominantV(m+i)transitioninvolves less autoionization/more directionization/HBr+formation

H + Br**(5s)