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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Presentation transcript:

HBr, (updated ; slide 12) V(m+i) /HBr+(v+) spectra analysis

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

BaselineType: Constant y0 = /- 0 Peak 0Type: Gauss Location = / Height = / Area = / FWHM = / Fit function parameters Location = / Width = / Height = / Peak 1Type: Gauss Location = / Height = / Area = / FWHM = / Fit function parameters Location = / Width = / Height = / Peak 2Type: Gauss Location = / Height = / Area = / FWHM = / Fit function parameters Location = / Width = / Height = / Fit completed 12:45 6. desember 2013 Y data wave: root:wave11[275, 322] X data wave: root:wave10 Chi square: Total fitted points: 48 Multi-peak fit version

HBr, V(m+5) Gr3, Lay3 HBr, V(m+5), J´= 0, Gaussian fits to HBr + (v + ) and HBr + * (v + ) peaks

BaselineType: Constant y0 = /- 0 Peak 0Type: Gauss Location = / Height = / Area = / FWHM = / Fit function parameters Location = / Width = / Height = / Peak 1Type: Gauss Location = / Height = / Area = / FWHM = / Fit function parameters Location = / Width = / Height = / Peak 2Type: Gauss Location = / Height = / Area = / FWHM = / Fit function parameters Location = / Width = / Height = / Peak 3Type: Gauss Location = / Height = / Area = / FWHM = / Fit function parameters Location = / Width = / Height = / Fit completed 13:12 6. desember 2013 Y data wave: root:wave11[257, 321] X data wave: root:wave10 Chi square: Total fitted points: 65 Multi-peak fit version

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 )

HBr, E(0), J´= 1, Gaussian fits to HBr + (v + ) and HBr + * (v + ) peaks Gr:4,Lay3

BaselineType: Constant y0 = / Peak 0Type: Gauss Location = / Height = / Area = / FWHM = / Fit function parameters Location = / Width = / Height = / Peak 1Type: Gauss Location = / Height = / Area = / FWHM = / Fit function parameters Location = / Width = / Height =0.106+/ Peak 2Type: Gauss Location = / Height = / Area = / FWHM = / Fit function parameters Location = / Width = / Height = / Peak 3Type: Gauss Location = / Height = / Area = / FWHM = / Fit function parameters Location = / Width = / Height = / Peak 4Type: Gauss Location = / Height = / Area = / FWHM = / Fit function parameters Location =1.957+/ Width = / Height = / Fit completed 16:02 7. desember 2013 Y data wave: root:wave1[240, 322] X data wave: root:wave0 Chi square: Total fitted points: 83 Multi-peak fit version 2.00 HBr, E(0), J´= 1, Gaussian fits to HBr + (v + ) and HBr + * (v + ) peaks Gr:4,Lay3

HBr, E(0), J´=1 BaselineType: Constant y0 = / Peak 0FWHM = / Peak 1FWHM = / Peak 2FWHM = / Peak 3FWHM = / Peak 4FWHM = / HBr, V(m+5), J´= 0 BaselineType: Constant y0 = /- 0 Peak 0FWHM = / Peak 1FWHM = / Peak 2FWHM = / Peak 3FWHM = / Summary:

 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 ( pdf ): 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 ppt/ ) E(0) (see HBr-E0-KER ppt/ ) V(m+5) (see PPT ppt/ ) 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?

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)