hcl, negative ion detections 1hv ion-pair spectra (slides 3-4)
DESCRIPTION
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) - PowerPoint PPT PresentationTRANSCRIPT
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
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.pdfIs dealing with E and V(v´=9,10,11)
https://notendur.hi.is/agust/rannsoknir/papers/jcp127-124304-07a.pdfHCl: 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 intermediatestates HCl was found to dissociate into the H++Cl− ion pair with over 20% relative yield.”
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
https://notendur.hi.is/agust/rannsoknir/papers/HCl/jcp99-4986-93.pdf
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
https://notendur.hi.is/agust/rannsoknir/papers/jcp127-124304-07a.pdf
NB!: Max contribution to H+ + Cl- formationFor v´=12, but significant contributionAlso from v´=11 and 13
H+ + Cl-
#
https://notendur.hi.is/agust/rannsoknir/papers/jcp127-124304-07a.pdf
https://notendur.hi.is/agust/rannsoknir/papers/HCl/jcp99-4986-93.pdf
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)?
130x103
120
110
100
90
80
E [
cm-1
]
43210
r [Å]
X(HCl+)
2
H+Cl*(4P)
H+Cl*(2P)
V <-- H+ + Cl
-
H*(2s2S)+Cl
H*(2p2P)+Cl
H+Cl*(4P)
H+Cl*(4D)H+Cl*(2D)
H+Cl*(2D)
E <-- H+Cl*(2P)F <-- H+Cl*(4S)
H+Cl*(2S/2P)
H+Cl*(4D)
H+Cl*(4F)H+Cl*(4P)
H+Cl*(2D) H+Cl*(2F)H+Cl*(2P)
H+Cl
H+Cl+H+ +Cl
Dye curveC480 (x4)
V(v´=12) 84747.1 cm-1
https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-260712ak.pxp
EF
86x103
84
82
80
E [
cm-1
]
4321
r [Å]
X(HCl+)
2 H+Cl*(4P)H+Cl*(2P)V <-- H+ + Cl
- H*(2s2S)+ClH*(2p2P)+Cl H+Cl*(4P)H+Cl*(4D) H+Cl*(2D)H+Cl*(2D)E <-- H+Cl*(2P)F <-- H+Cl*(4S)H+Cl*(2S/2P) H+Cl*(4D)H+Cl*(4F)H+Cl*(4P)H+Cl*(2D) H+Cl*(2F)H+Cl*(2P)
H+Cl
H+Cl+H+ +Cl
Dye curveC480(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
v´=0
We should be able to scan V(v´=11,12 13) by use of Dye: 480
http://www.raunvis.hi.is/~agust/rempisvaedidir/jcp109585698.pdf
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!
4
3
2
1
0
x106
84.7484.7284.7084.6884.6684.6484.62x10
3
84734.0 (Q(J´=J´´=1))
e-
H-
(2+n)REMPI, HiCl; i = 35,37V(v´=12,J´) <-<- X(v´=0,J´´)Q lines
https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Layout:2, Graph:7
2hv/cm-1
i=35
i=37
60
50
40
30
20
10
0
x103
3020100
35Cl+H35Cl+
H-
H+
35Cl- 37Cl-
CnHm+...
e-
(slide 15) (slide 16)
Mw
(slide 17)HiCl; i = 35,3784734.0 cm-1 (Q(1))
https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:1, Gr:6
14
13
12
11
x10
3
3029282726252423222120191817161514131211
C-
CH-
CH2-
C2-
C2H-O-/CH4
- (?)
OH-(?)
HiCl; i = 35,3784734.0 cm-1 (Q(1))
https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:1, Gr:6
(?)
Mw
12
10
8
6
4
2
0
-2
-4
x10
3
4442403836343230
35Cl+H35Cl+
35Cl- 37Cl-
Mw
HiCl; i = 35,3784734.0 cm-1 (Q(1))
https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:1, Gr:6
60
50
40
30
20
10
0
x10
3
1.41.21.00.80.60.40.20.0-0.2
https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:1, Gr:6
H-
H+
e-
Mw
HiCl; i = 35,3784734.0 cm-1 (Q(1))
4
3
2
1
0
x10
6
84.7484.7284.7084.6884.6684.6484.62x10
3
1D-REMPI spectra:
https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:3, Gr:8
e-
35Cl-
35Cl- smoothed
Q(2)i = 35
Q(1)i = 35
• Main 35Cl- signals seem to appear for Q(1) and Q(2)
25
20
15
x103
3020100
12.0
11.8
11.6
11.4
11.2
11.0
10.8
x103
3837363534
HiCl; i = 3584746.8 cm-1 (Q(0))
4
3
2
1
0
x10
6
84.7484.7284.7084.6884.6684.6484.62x10
3
https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:6, Gr:16
35Cl-
Mw
60
50
40
30
20
10
0
x103
3020100
35Cl+H35Cl+
35Cl- 37Cl-
Mw
HiCl; i = 3584734.0 cm-1 (Q(1))
https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:1, Gr:6
4
3
2
1
0
x10
6
84.7484.7284.7084.6884.6684.6484.62x10
3
12.2
12.0
11.8
11.6
11.4
11.2
11.0
x10
3
39.539.038.538.037.537.036.536.035.535.034.534.033.533.0
35Cl-
37Cl-
50
40
30
20
10
x103
403020100
35Cl-
(slide 21)
HiCl; i = 3584708.4 cm-1 (Q(2))
https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:4, Gr:10
Mw
4
3
2
1
0
x10
6
84.7484.7284.7084.6884.6684.6484.62x10
3
12.0
11.5
11.0
10.5
x10
3
3837363534
35Cl-
50
40
30
20
10
x103
3020100
HiCl; i = 3584670.1 cm-1 (Q(3))
12.0
11.8
11.6
11.4
11.2
11.0
10.8
10.6
x10
3
3837363534
4
3
2
1
0
x10
6
84.7484.7284.7084.6884.6684.6484.62x10
3
https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:5, Gr:13
35Cl-
Mw
25
20
15
10
x103
403020100
11.6
11.4
11.2
11.0
10.8
x10
3
39383736353433
4
3
2
1
0
x10
6
84.7484.7284.7084.6884.6684.6484.62x10
3
HiCl; i = 3784729.6 cm-1 (Q(1))
https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:7, Gr:15
No 35Cl- signalPossibly some 37Cl- (?)
37Cl- (?)
Mw
60
50
40
30
20
x103
1.21.00.80.60.40.20.0
H-
e-
i=35
i=37; Q(1)
Mw
https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:8, Gr:17
Small but significant time delay for i= 37relative to that for i = 35 (?)
Q(0)
Q(4)
Q(1)
Q(3)
Q(2)
13.5
13.0
12.5
12.0
11.5
11.0
x103
14.514.013.513.012.512.011.5
Small but significant time delay for i= 37relative to that for i = 35
https://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)
13.0
12.5
12.0
11.5
11.0
x103
19181716
Small but significant time delay for i= 37relative to that for i = 35
https://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)
12.2
12.0
11.8
11.6
11.4
11.2
11.0
10.8
x103
38373635
NO delay(??) for i= 37relative to that for i = 35
Mw
35Cl-
37Cl-
37Cl-(?)
https://notendur.hi.is/agust/rannsoknir/rempi/hcl/July12/PXP-280712ak.pxp ; Lay:8, Gr:17
i=35, Q(0-4)
i=37; Q(1)
Comments/suggestions:
•Although not quite clear it looks as if the Cl- signals are formed in a differentway to that of other negative ions (CnHm+,...), most likely as2hv + 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)
