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.pdfhttps://notendur.hi.is/agust/rannsoknir/papers/HBr/pccp8-2940-06.pdf (HBr) http://www3.hi.is/~agust/rannsoknir/papers/jcp120-767-04.pdfhttp://www3.hi.is/~agust/rannsoknir/papers/jcp120-767-04.pdf (HCl) https://notendur.hi.is/agust/rannsoknir/papers/jcp127-124304-07a.pdfhttps://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.pdfhttps://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.pdfhttps://notendur.hi.is/agust/rannsoknir/papers/HCl/jcp99-4986-93.pdf : 85.98 nm https://notendur.hi.is/agust/rannsoknir/papers/HCl/jcp99-4986-93.pdf

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

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

6. https://notendur.hi.is/agust/rannsoknir/papers/jcp127-124304-07a.pdf https://notendur.hi.is/agust/rannsoknir/papers/HCl/jcp99-4986-93.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)nl  (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 https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-260712ak.pxp EF

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

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

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

15. C-C- CH - CH 2 - C2-C2- C2H-C2H- O - /CH 4 - (?) OH - (?) H i Cl; i = 35,37 84734.0 cm -1 (Q(1)) https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxphttps://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:1, Gr:6 (?) Mw

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

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

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

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

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

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

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

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

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

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

26. 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.pxphttps://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:8, Gr:17 Mw i=35, Q(0-4) i=37; Q(1)

27. 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.pxphttps://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:8, Gr:17 Mw i=35, Q(0-4) i=37; Q(1)

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

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)