HCl, negative ion detections
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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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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)

  • 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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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.”


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

https://notendur.hi.is/agust/rannsoknir/papers/HCl/jcp99-4986-93.pdf

https://notendur.hi.is/agust/rannsoknir/papers/jcp127-124304-07a.pdf


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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)?


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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!


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

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


Hcl negative ion detections 1hv ion pair spectra slides 3 4

  • 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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