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H35Cl and H37Cl Intensity Ratio Analysis and Comparison

This analysis compares the intensity ratios of H35Cl and H37Cl for different J' levels and v' values. It includes the evaluation of coupling strength and least square minimization. The results highlight the importance of the gamma parameter and the effect of different W12 values.

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H35Cl and H37Cl Intensity Ratio Analysis and Comparison

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  1. H35Cl, j(0+) intensity ratio analysis and comparison of experimental data agust,www,....Jan11/PPT-210111ak.ppt agust,heima,...Jan11/Evaluation of coupling strength j state-2i0111kmak.xls agust,heima,....Jan11/PXP-210111ak.pxp The following holds for W12 = 25 cm-1:

  2. g = 0.0171 Least square minimization of I(35Cl+)/I(H35Cl+) vs J´ (for J´=0-5) with respect to a and g least sq. error (J=0-5) ag error 2 0.0171 0.000441 2.2 0.0149 0.000333 2.5 0.0124 0.000245 3 0.0092 0.000306 g = 0.0149 g = 0.0092 g = 0.0124 a Agust,heima,....Jan11/PXP-210111ak.pxp; Lay: 0, Gr:0

  3. exp Calc.(v´=19-22) least sq. error (J=0-5) 0 3 5 J´ g = 0.0149 v´=19,20,21,22 and sum 0 3 5 J´ v´=18,19,20,21,22,23 and sum a Agust,heima,....Jan11/PXP-210111ak.pxp; Lay: 0, Gr:0 agust,heima,...Jan11/Evaluation of coupling strength j state-210111kmak.xls

  4. exp Calc.(v´=19-22) least sq. error (J=0-5) 0 3 5 J´ v´=19,20,21,22 and sum 0 3 5 J´ g = 0.0124 a Agust,heima,....Jan11/PXP-210111ak.pxp; Lay: 0, Gr:0 & agust,heima,...Jan11/Evaluation of coupling strength j state-210111kmak.xls

  5. exp Calc.(v´=19-22) least sq. error (J=0-5) 0 3 5 J´ v´=19,20,21,22 and sum 0 3 5 J´ g = 0.0092 a Agust,heima,....Jan11/PXP-210111ak.pxp; Lay: 0, Gr:0 agust,heima,...Jan11/Evaluation of coupling strength j state-210111kmak.xls

  6. 1) NB!: contributions from v´< 20 and v´> 21 CLEARLYCAN NOT BE IGNORED!!! • This analysis assumes W12 to be constant and independent with v´(ip) and to be the • same value as that derived from shift analysis for v´(ip)=21. a and g are also • assumed to be constant and independent with v´(ip) : Thus least square analyses on • a and g (for W12 = 25 cm-1) resulted in • W12 = 25 cm-1 • a = 2.5 • = 0.0124 for j(0+) H35Cl The significantly larger g value, compared to that observed for other triplet states (g = 0.002 – 0.004) might be because of a large contribution to the dissocaiation Channels from photodissociation follwed by Cl ionization, i.e. 2hv + HCl ->-> HCl*(j(0+),v´=0, J´) HCl*(j(0+),v´=0, J´) + hv -> HCl** -> H + Cl* Cl* + hv -> Cl+ + e- Analogous analysis now need to be done for H37Cl!!!!!

  7. The J’ = 6 peak is problematic for H35Cl since the mass peaks for J’ = 6 and 8 overlap. Hence the experimentally evaluated ion ratio for J’ = 6 will be an underestimated value. Therefore it is acceptable that the calculated ratio is higher. This should not be the problem for H37Cl. Lets try to include v´=18 and 23 interactions:

  8. exp Calc.(v´=18-23) J´ v´=18,19,20,21,22,23 and sum J´ W12 = 25 cm-1; a = 1.7; g = 0.0135 agust,heima,...Jan11/Evaluation of coupling strength j state-220111kmak.xls

  9. It is interesting to see that the contribution falls down very slowly as DE(J´) • increases / v´ “moves further away” from the Rydberg state. • But what happens if W12 changes with v´, say W12 increases? • I tried • W12= 22,23,24,25,26,27 vs v´=18,19,20,21,22,23 & • W12= 19,21,23,25,27,29 vs v´=18,19,20,21,22,23 & • W12= 28,27,26,25,24,23 vs v´=18,19,20,21,22,23 & • W12= 31,29,27,25,23,21 vs v´=18,19,20,21,22,23 • No big change • Looking at calculations such as in the previous figure shows that contribution • from v´< 20 and v´>21 is close to a constant (f). Therefore the relevant expression for • I(Cl+)/I(HCl+) is • Is it perhaps possible to obtain good fit for the parameters a and f only • assuming g to be zero?

  10. No that does not seem to be the case. In other words gamma is an important parameter. Looking at: It is clear that c22 is very small and the ratio for v´<20 and v´> 21 is simply: NB! It is interesting to see that similar g values are obtained independet of the number of v´(V) contribution: g = 0.013 for v´=20-21 (KM) g = 0.0124 for v´= 19-22 g = 0.0135 for v´= 18-23 THIS IS IMPORTANT!

  11. Effect of g is clearly seen below:

  12. W12= 25, a = 1.7 How can I make the colors in the excel graph to stay unchanged? g = 0 J´ v´=18,19,20,21,22,23 and sum g = 0.006 J´ g = 0.013 J´ agust,heima,...Jan11/Evaluation of coupling strength j state-220111kmak.xls

  13. W12=25, f = 1 Minimize with respect to a and g=> a = 2.2, g = 0.0198, least sq. error(J´=0-5) = 0.000706 NB!: As a rough estimate I increased The experimental Ratio value to 0.5 We realy need to analogous test on H37Cl where the peak overlap problem does not exist. J´ agust,heima,...Jan11/Evaluation of coupling strength j state-220111kmak.xls

  14. Lets´ compare the calc. sum values for different optimizaed g values: Is the graph shape perhaps comparable?: Lets look at plots normalized to the largest peak (i.e. J´=6) See note from 230111: Fit of Irel(exp) = (I(Cl+)/I(HCl+)(J´;exp))/(I(Cl+)/I(HCl+)(J´max;exp)) vs J´ by Irel(calc)= (I(Cl+)/I(HCl+)(J´;calc))/(I(Cl+)/I(HCl+)(J´max;calc)) vs J´ Thus the a parameter drops out NB!: J´max = 6 All give equally good fit (see figure next slide) ERGO: 1) Use f = 0 (i.e. Neglect f*a*g) 2) Use only v´= 20 & 21 and perform fit on Irel (exp) vs J´ by varying g only!!! agust,heima,...Jan11/Evaluation of coupling strength j state-230111kmak.xls

  15. Fit of Irel(exp) = (I(Cl+)/I(HCl+)(J´;exp))/(I(Cl+)/I(HCl+)(J´max;exp)) vs J´ by Irel(calc)= (I(Cl+)/I(HCl+)(J´;calc))/(I(Cl+)/I(HCl+)(J´max;calc)) vs J´ : Relative Intensity ratios J´ agust,heima,...Jan11/Evaluation of coupling strength j state-230111kmak.xls

  16. Comparison of KM´s and JL´s ion ratios for j(0+), H35Cl: agust,heima,...Jan11/Evaluation of coupling strength j state-240111kmak.xls

  17. JL 151210 JL 161210 KM J´ agust,heima,...Jan11/Evaluation of coupling strength j state-240111kmak.xls

  18. JL 161210 JL 151210 KM J´ agust,heima,...Jan11/Evaluation of coupling strength j state-240111kmak.xls

  19. Conclusion concerning H35Cl j(0+): J´ 5 6 7 W12=25, a=2.111, g = 0.0319 (f=0):

  20. agust,heima,...Jan11/Evaluation of coupling strength j state-270111kmak.xls

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