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HCl Deperturbation E1 V14 V15: Perturbation Analysis and Distortion Measures

This document provides instructions and information on performing deperturbation calculations for HCl using E1, V14, and V15 levels. It also discusses the correlation between distortion measures B1 and D1, and the effect of different parameters on the energy levels.

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HCl Deperturbation E1 V14 V15: Perturbation Analysis and Distortion Measures

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  1. HCl, Deperturbation E1, V14, V15 (slides 2-7 ) E0, V10, V11 (slides 8-10 ) https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PPT-300712ak.ppt https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/XLS-300712ak.xls https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-300712ak.pxp https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-010812ak.pxp Instruction about how to perform deperturbation calculations: https://notendur.hi.is/jil3/Instruction/Deperturbedprocedure.htm &https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/DOC-020812jla.doc Information sheet (for HCl, Ei; i = 0,1 & V(v´); v = 10,11,14,15): https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/DOC-020812jl.doc

  2. v1,v2,v3 V15 E1 V14 Unrealistic region 123 W/cm-1 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-300712ak.pxp Lay:0, Gr:0

  3. HCl, E1, V14, V15 B1 Unrealistic region 123 W/cm-1 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-300712ak.pxp Lay:1, Gr:1

  4. HCl, E1, V14, V15 D1 Deviation of D1 from 0 is a resonable measure of distortion, i.e. one might expect D1 (unperturbed) to be close to zero analogous to that for X(HCl) (De= 5.3194E-4 = 0.53E-3=+0.00053<= NIST) and X(HCl+) (De= 5.477E-4 = 0.547E-3=+0.000547<= NIST ) Unrealistic region 123 W/cm-1 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-300712ak.pxp Lay:2, Gr:2

  5. HCl, E1, V14, V15 W12(max)=DE/2 = 246/2= https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/XLS-300712ak.xls

  6. HCl, E1, V14, V15 D1 +0.000596! 0 -6.71E-05 -0.00078 124.6 W/cm-1 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-300712ak.pxp Lay:3, Gr:3

  7. HCl, E1, V14, V15 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/XLS-300712ak.xls

  8. B1 ( ) ( ) ( ) ( ): unrealistic points ( ) D1 => correlation between B1 and D1, i.e. highest B1 value for D1 closest to 0 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-300712ak.pxp Lay:8, Gr:8

  9. HCl, E0, V10, V11 v1,v2,v3 V11 E0 83697 Unrealistic region V10 W/cm-1 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-300712ak.pxp Lay:7, Gr:7

  10. HCl, E0, V10, V11 B1 W/cm-1 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-300712ak.pxp Lay:4, Gr:4

  11. HCl, E0, V10, V11 D1 W/cm-1 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-300712ak.pxp Lay:5, Gr:5

  12. HCl, E0, V10, V11 B1 D1 => correlation between B1 and D1, i.e. highest B1 value for D1 closest to 0 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-300712ak.pxp Lay:6, Gr:6

  13. HCl, E0, V10, V11 No significant change in D(v1) https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/XLS-300712ak.xls

  14. Let´s perform dep. calculations for different W´s (i.e. WH¹ WL) for E1,V14, V15:

  15. HCl, E1, V14, V15 for W2 = 123 v1 W3 / WH https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-010812ak.pxp; Lay:2, Gr:2

  16. HCl, E1, V14, V15 for W2 = 123 B1 W3 / WH https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-010812ak.pxp; Lay:0, Gr:0

  17. HCl, E1, V14, V15 for W2 = 123 D1 D(D1) = 0 – 0.001 cm-1 W3 / WH https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-010812ak.pxp; Lay:1, Gr:1

  18. HCl, E1, V14, V15 for W2 = 123, W3 CHANGES as above B1 D(D1) = 0 – 0.001 cm-1 D1 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-010812ak.pxp; Lay:3, Gr:3

  19. HCl, E1, V14, V15 for W2 = 123, W3 CHANGES Only small increase in W3 from 123 to about 129 (for W2 = 123) -improves D1 (= +0.0006 cm-1) -increases B1 from 9.97 to 10,096 cm-1 -causes small increase in v1 ( 85845 -> 85848 cm-1) https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/XLS-300712ak.xls

  20. I tried • –to fix D1, and to vary W2 & W3 => W2 = 123 W3 = 110 +/- big error (typically)! • - to use W2 = 125 and to vary W3 => W3 ca. 125 best!

  21. Now let´s check E0,....: Comparison with Fields work: https://notendur.hi.is/agust/rannsoknir/papers/HCl/jcp109-8374-98.pdf: Try this

  22. v1 W3 / WH https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-020812ak.pxp ; Lay:6, Gr:6

  23. HCl, E0, V10, V11 for W2 = 187 B1 W3 / WH https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-020812ak.pxp ; Lay:4, Gr:4

  24. HCl, E0, V10, V11 for W2 = 187 D1 D(D1) = 0 – 0.001 cm-1 W3 / WH https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-020812ak.pxp ; Lay:5, Gr:5

  25. HCl, E0, V10, V11 for W2 = 187, W3 CHANGES as above B1 D1 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-020812ak.pxp ; Lay:7, Gr:7

  26. No significant change in D(v1) https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/XLS-300712ak.xls

  27. Now it looks like: 1) E1: B1= 10.10, D1 = +0.0006 , W2 = 123, W3 = 129 2) E0: B1= 9.01, D1= +0.0004, W2 = 187, W3= 193.5 2) Could it be that W2 <187 and W3 > 193.5 For E0, V10,V11? Search for D1 <0.001 and B1 > 9.01 for E0, V10,V11 => By trying W2 =180 and varying W3 > 180 => B1(max)= 8.37 only for D1(min) = -0.0051 (for W3 = 197) and V1= 83755 (which is even higher and makes D(v1) still smaller Ergo: this is not convincing Could W2 > 187 and W3 still higher? Tried: W2=190 and varying W3 >190 =>B1(max)= 9.1 for D1(min) = 0 (for W3 = 193) and V1 = 83700 => no big change in D(v1) & Tried: W2 = 195 and varying W3 > 195 =>B1(max)=9.2 for D1(min) = -0.0009 (NB D1 <0, always)V1 = 83709 => no big change in D(v1) Best Results! In agreement with Field et al.! No improvements! See: https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/XLS-300712ak.xls

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