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HCl, negative ion detections 1hv ion-pair spectra (slides 3-4)

HCl, negative ion detections 1hv ion-pair spectra (slides 3-4) Loock´s prediction about H+ + Cl- formation channels(slides 5-6) Energetics vs Dye for V(v´=...12...) (slides 8-10) Cl- via E(v´=0) excitation(?) (slides 11-12) First neg. Ion detections (slides 13-21)

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HCl, negative ion detections 1hv ion-pair spectra (slides 3-4)

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  1. HCl, negative ion detections • 1hv ion-pair spectra (slides 3-4) • Loock´s prediction about H+ + Cl- formation channels(slides 5-6) • Energetics vs Dye for V(v´=...12...) (slides 8-10) • Cl- via E(v´=0) excitation(?) (slides 11-12) • First neg. Ion detections (slides 13-21) • V(v´=12), Q(1), Mass spectra (slides 14-17) • V(v´=12), Q(0-3), i=35,37; Mass spectra (slides 20-24) • i=37 vs 35 time delay(?) (slides 25-28) • https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PPT-260712ak.ppt

  2. Loock´s papers: https://notendur.hi.is/agust/rannsoknir/papers/HBr/pccp8-2940-06.pdf (HBr) http://www3.hi.is/~agust/rannsoknir/papers/jcp120-767-04.pdf (HCl) https://notendur.hi.is/agust/rannsoknir/papers/jcp127-124304-07a.pdf (HCl & HBr) http://www3.hi.is/~agust/rannsoknir/papers/jcp120-767-04.pdf Is dealing with E and V(v´=9,10,11) https://notendur.hi.is/agust/rannsoknir/papers/jcp127-124304-07a.pdf HCl: dealing with E(0) and V(9,11-13,15) & g(0) HBr: dealing with E(0) and V(m+3,m+5 to m+8) & H(0) https://notendur.hi.is/agust/rannsoknir/papers/jcp127-124304-07a.pdf: “For selected intermediate states HCl was found to dissociate into the H++Cl− ion pair with over 20% relative yield.”

  3. Our paper (´93): https://notendur.hi.is/agust/rannsoknir/papers/HCl/jcp99-4986-93.pdf : 85.98 nm 85.98 nm https://notendur.hi.is/agust/rannsoknir/papers/HCl/jcp99-4986-93.pdf

  4. 78.66 nm 127120.7cm-1: thr. For (2+1)REMPI for V(v´=12) See: http://www.hi.is/~agust/rannsoknir/rempi/hcl/HCl,agust07-/HCl-exc.transitions-060907.ppt 116305.1cm-1 H+ + Cl- threshold https://notendur.hi.is/agust/rannsoknir/papers/HCl/jcp99-4986-93.pdf

  5. H+ + Cl- NB!: Max contribution to H+ + Cl- formation For v´=12, but significant contribution Also from v´=11 and 13 # https://notendur.hi.is/agust/rannsoknir/papers/jcp127-124304-07a.pdf

  6. https://notendur.hi.is/agust/rannsoknir/papers/HCl/jcp99-4986-93.pdfhttps://notendur.hi.is/agust/rannsoknir/papers/HCl/jcp99-4986-93.pdf https://notendur.hi.is/agust/rannsoknir/papers/jcp127-124304-07a.pdf

  7. NB!: If Loocks interpretation in # (see above slide 5) is correct, i.e. that Cl- formation occurs via bound to bound transition,V(v´=12 ) -> (A)nls (Rydberg state), the Cl- formation should be greatly J´ dependent! NB!: they used Q(J´=0) and Q(J´=1) lines only. Idea: Could it be that the H+ + Cl- formation is mainy J´ dependent (and less v´ dependent)?

  8. Dye curve C480 (x4) V(v´=12) 84747.1 cm-1 F E https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-260712ak.pxp

  9. Dye curve C480 (X4) V(v´=13);85278.4 cm-1 V(v´=12); 84747.1 cm-1 V(v´=11) 84208 cm-1 v´=0 v´=0 E V F https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-260712ak.pxp

  10. We should be able to scan V(v´=11,12 13) by use of Dye: 480

  11. http://www.raunvis.hi.is/~agust/rempisvaedidir/jcp109585698.pdfhttp://www.raunvis.hi.is/~agust/rempisvaedidir/jcp109585698.pdf

  12. E(v´=0) mixes strongly with V(v´=11) Therefore, one might expect to see Cl- formation via excitation to E(v´=0) as well!

  13. 84734.0 (Q(J´=J´´=1)) (2+n)REMPI, HiCl; i = 35,37 V(v´=12,J´) <-<- X(v´=0,J´´) Q lines i=35 e- i=37 H- 2hv/cm-1 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Layout:2, Graph:7

  14. HiCl; i = 35,37 84734.0 cm-1 (Q(1)) (slide 17) H- H+ CnHm+... (slide 15) (slide 16) e- 35Cl- 37Cl- H35Cl+ 35Cl+ Mw https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:1, Gr:6

  15. HiCl; i = 35,37 84734.0 cm-1 (Q(1)) CH- O-/CH4- (?) C2H- (?) OH-(?) C- C2- CH2- Mw https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:1, Gr:6

  16. 35Cl- 37Cl- HiCl; i = 35,37 84734.0 cm-1 (Q(1)) H35Cl+ 35Cl+ Mw https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:1, Gr:6

  17. HiCl; i = 35,37 84734.0 cm-1 (Q(1)) e- H- H+ Mw https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:1, Gr:6

  18. Q(1) i = 35 1D-REMPI spectra: Q(2) i = 35 e- 35Cl- 35Cl- smoothed https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:3, Gr:8

  19. Main 35Cl- signals seem to appear for Q(1) and Q(2)

  20. HiCl; i = 35 84746.8 cm-1 (Q(0)) 35Cl- Mw https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:6, Gr:16

  21. HiCl; i = 35 84734.0 cm-1 (Q(1)) 35Cl- 37Cl- 35Cl- 37Cl- H35Cl+ 35Cl+ Mw https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:1, Gr:6

  22. HiCl; i = 35 84708.4 cm-1 (Q(2)) 35Cl- (slide 21) 35Cl- Mw https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:4, Gr:10

  23. HiCl; i = 35 84670.1 cm-1 (Q(3)) 35Cl- Mw https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:5, Gr:13

  24. HiCl; i = 37 84729.6 cm-1 (Q(1)) 37Cl- (?) Mw No 35Cl- signal Possibly some 37Cl- (?) https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:7, Gr:15

  25. Q(1) Q(3) e- i=35 H- Q(2) Q(4) i=37; Q(1) Q(0) Mw Small but significant time delay for i= 37 relative to that for i = 35 (?) https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:8, Gr:17

  26. i=35, Q(0-4) i=37; Q(1) Mw Small but significant time delay for i= 37 relative to that for i = 35 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:8, Gr:17

  27. i=35, Q(0-4) i=37; Q(1) Mw Small but significant time delay for i= 37 relative to that for i = 35 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:8, Gr:17

  28. 35Cl- i=35, Q(0-4) 37Cl- 37Cl-(?) i=37; Q(1) Mw NO delay(??) for i= 37 relative to that for i = 35 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:8, Gr:17

  29. Comments/suggestions: • Although not quite clear it looks as if the Cl- signals are formed in a different • way to that of other negative ions (CnHm+,...), most likely as • 2hv + HCl -> [H+Cl-]*(V(12,J´)) [H+Cl-]*(V(12,J´))+hv -> ..-> H+ + Cl- • Let´s improve signals. • Check HCl*(V(v´=11)), which ought to show H+ + Cl- ion formations also(see slide 5) • Since E(v´=0) mixes strongly with V(v´=11), excitation via E(0) might also show • Cl- ions (NB!: E(0) is reachable by C480; see slide no. 9) • Since F(v´=0) is “pure” Rydberg state and does not mix with the V state it should • show NO H+ + Cl- (NB!: F(0) is reachable by C480; see slide no. 9)

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