1. HBr
Mass resolved REMPI
and
Imaging REMPI

2. E
H + X+ + e J+ v+
HX+ + e
H + X**
IE(HX) J´ v´
(2+1)REMPI:
2hn + HX ->-> HX**(v´,J´)
1hn + HX** -> HX+(v+,J+)
HX**
Rydb.
H + Br/Br* HX
J´´
v´´= 0
r(HX)

3. E
H + X+ + e J+ v+
HX+ + e
H + X** J´ v´
(2+2)REMPI:
2hn + HX ->-> H+X-(v´,J´)
2hn + H+X- -> H + X+
HX**
v´,J´
Rydb.
H+X-/Ion-pair/V
H + Br/Br* HX
J´´
v´´= 0
r(HX)

6. HCl, F1D2 Q
Intensity
J´=J´´ = 9 8 7 6 5 4 3 2
H35Cl+
35Cl+
2hn / cm-1

7. e- HX REMPI: HX+ X+ H X ** H+--X- HX Energy IE limit J´ J´ v´ v´
r(H-X)

8. E
Interactions ?
State

9. E Interactions ? State (1) / y0 (2) / y0 c1y0 y c2y0 c1´y0 c2´y0 c1 c2
Fraction Rydb.
Fraction ion-pair
c1y0 1 y a
c2y0 2 = + b
c1´y0
c2´y0 - c1 c2
= 1

10. E Interaction W12: strength (1) / y0 (2) / y0 y c1y0 c2y0 c1 c2 y
Fraction Rydb.
Fraction ion-pair 1 2 2 2 y
c1y0
c2y0 c1 c2 + +
= 1 = a 1 2 y
c1´y0
c2´y0 - = b 1 2

11. E( ) E(J´) E (1) / y0 (2) / y0 y c1y0 c2y0 c1 c2 y c1´y0 c2´y0 DE
Fraction Rydb. 1 2
Fraction ion-pair 2 2 y
c1y0
c2y0 c1 c2 + +
= 1 = a 1 2 y
c1´y0
c2´y0 - = b 1 2

12. I.e. Mixing (c12 and c22) J´ dependent:
HCl:
V1S
F1D2 x

13. HX+ X+ E( ) E(J´) E (1) / y0 (2) / y0 y c1y0 c2y0 c1 c2 y c1´y0 c2´y0
Fraction Rydb. 1 2
Fraction ion-pair 2 2 y
c1y0
c2y0 c1 c2 + +
= 1 = a 1 2 y
c1´y0
c2´y0 - = b 1 2

14. F, v´= X, v´=0
H35Cl
H37Cl
I(Cl+)/I(HCl+) J´

15. Q HCl, F1D2 Com- press- ion E x p a n s i o n Intensity J´=J´´ = 9 8 76 5 4 3 2
H35Cl+
35Cl+
2hn / cm-1

16. DE

17. Above: Weak „near-resonance“ state interaction (W12 small)
Below: Strong „off-resonance interaction“

18. H79Br

19. E
H + X+ + e J+ v+
HX+ + e
H + X** J´
v´=
v´=m+5
v´=m+4
HX** E
H+X- /Ion-pair/V
H + Br/Br* HX
J´´
v´´= 0
r(HX)

20. E
H + X+ + e J+ v+
HX+ + e
H + X** J´
v´=
v´=m+5
v´=m+4
HX** E
H+X- /Ion-pair/V
H + Br/Br* HX
J´´
v´´= 0
r(HX)

21. H79Br V 1S(0+) J´=9 W´=0 W´=0 J´=6 v´=m+5 Off resonance J´=0 J´=6
E/cm-1
J´=6
J´=0
E 1S(0+), v´=0
J´=0

22. E(0)
Exp:
Calc:

24. H79Br V 1S(0+) J´=9 J´=6 v´=m+5 J´=0 J´=6 J´=9 v´=m+4 E/cm-1 J´=6 J´=0
E 1S(0+), v´=0
J´=0

25. Imaging experiments in Crete:

26. Suggestions for experiments:
-relevant to our studies (see above):
Studies relevant to strong state interactions vs. J´
( /JCP; 2013) (or
Record ion images (H+, Br+, HBr+ (?)) vs J´ for two-photon, one-color resonance excitations to J´ levels of
The Rydberg state E(v´=0); For Q lines, J´=0, 2, ..8, 9(?)
The Ion-pair state V(v´=m+5); For Q lines, J´=0, 2, ..8, 9(?)
The Ion-pair state V(v´= m+4); For Q lines, J´=0, 2, ..8, 9(?)
(excitation range: – cm-1/ eV; photons: nm;
see lines: and/or :

27. 2) Studies relevant to i) weak resonance state interactions and ii) strong interactions vs. J´ ( /JCP, 2012)
(or )
Record ion images (H+, Br+, HBr+ (?)) vs J´ for two-photon one color resonance excitations to J´ levels of
a) The Rydberg state F(v´=1); Q lines, J´=3, 4,5,6,7 (i) b) The Rydberg state E(v´=1); Q lines, J´= 0,1,….7(?) (ii) c) The Rydberg state H(v´=0), Q lines, J´= 0,1,….9(?) (ii)
d) The Ion-pair state V(v´=m+7), Q lines, J´= 0,1, ..(5),..9 (i and ii) e) The Ion-pair state V(v´=m+8), Q lines, J´= 0,1,…7 (ii) (excitation range cm-1/9.80 – 9.96 eV; photons: nm;
see lines:
and/or
and/or

28. H+
Br+ and Br+ from Br resonances
Br- (<= H+ + Br-)

31. How are the H+ ´s formed?

32. H+ + Br(3/2)
[22P] 1S0,3P0
[ B2S ]..
H* + Br*(1/2)
H* + Br (3/2)
H+ + Br-
[ 4P,5s ] 3P0
H + Br**(5s)
V/Ion-pair Ry

33. H+ + Br (3/2)/Br*(1/2)
[22P]..
[ B2S ]..
HBr+(v+)(3/2,1/2)
H* + Br*(1/2)
H* + Br (3/2)
H+ + Br -
H + Br**(5s)
[ 4P,5s ] 3P0
V/Ion-pair Ry

34. H+ + Br*(1/2)
[22P] 1S0,3P0
[ B2S ]..
H* + Br*(1/2)
H* + Br (3/2)
H+ + Br-
H + Br**(5s)
[ 4P,5s ] 3P0
V/Ion-pair Ry

35. HBr+(A2S+)
HBr***
[A2S+]..
HBr+(X2P)
H+ + Br-
V/Ion-pair Ry

36. In summary (?):
H+ + Br-
….via HBr***/H+Br- (2+1) hn
….via HBr+(v+) (2+2) hn
….via H* + Br/Br* (2+2) hn
H+ + Br (3/2)/Br*(1/2)
H+ + Br(3/2,1/2)
H+ + Br*(1/2, 3/2)
V/Ion-pair Ry

37. Imaging experiments / data

38. HBr, E(v´=0), J´= 1
J´= 1,2,…….

39. J´= 10(?) 9 8 7 6 5 4 3 2 1
KER/eV

40. Signal predictions

41. H+ + Br(3/2,1/2)
H+ + Br*(1/2, 3/2)
….via H* + Br/Br* (2+2) hn

42. H+ + Br*(1/2) E
H+ + Br (3/2)
H + Br+ + e
KER(3/2)
KER(1/2)
HBr+ + e
H* + Br*(1/2)
H* + Br (3/2)
H + Br**
SO(Br*)
HBr**
3hn
E(H*)
H+Br-
H + Br
D0(HBr)
HBr
E(J´´)
E(J´´)+3hn = D0(HBr) +E(H*)+KER(3/2) => KER(3/2)=3hn + E(J´´)–D0(HBr)-E(H*)
E(J´´)+3hn = D0(HBr) +E(H*)+KER(3/2) + SO(Br*) => KER(1/2)=3hn + E(J´´)–D0(HBr)-E(H*)-SO(Br*)

43. H+ + Br(3/2,1/2)
H+ + Br*(1/2, 3/2)
….via H* + Br/Br* (2+2) hn
KER(3/2)=3hn + E(J´´)–D0(HBr)-E(H*)
KER(1/2)=3hn + E(J´´)–D0(HBr)-E(H*)-SO(Br*)
E(J´´) = B´´(J´´(J´´+ 1)) – D´´J´´2(J´´+ 1)2
H+ + Br-
….via HBr***/H+Br- (2+1) hn
KER= 3hn + E(J´´) – D0(HBr) - IE(H) + EA(Br)

44. HBr, E(0):
H+ +
Br(3/2)
J´= 10 9 8 7 6 5 4 3 2 1
Predicted KER´s
For H+ + Br-
H+ +
Br(1/2)
KER/eV
KER/eV

45. H+ + Br(3/2,1/2)
H+ + Br*(1/2, 3/2)
….via H* + Br/Br* (2+2) hn
KER(3/2)=3hn + E(J´´)–D0(HBr)-E(H*)
KER(1/2)=3hn + E(J´´)–D0(HBr)-E(H*)-SO(Br*)
E(J´´) = B´´(J´´(J´´+ 1)) – D´´J´´2(J´´+ 1)2
H+ + Br-
….via HBr***/H+Br (2+1) hn
KER= 3hn + E(J´´) – D0(HBr) - IE(H) + EA(Br)
H+ + Br (3/2)/Br*(1/2)
….via HBr+(3/2,v+)/HBr+(1/2,v+) (2+2) hn
KER(3/2<- 3/2)= hn + IE(HBr+ (3/2)) + G0(HBr+ (3/2),v+) –D0(HBr) - IE(H) KER(1/2<- 3/2)= hn + IE(HBr+ (3/2)) + G0(HBr+ (3/2),v+) –D0(HBr) - IE(H)-SO(Br*)
KER(3/2<- 1/2)= hn + IE(HBr+ (1/2)) + G0(HBr+ (1/2),v+) –D0(HBr) - IE(H) KER(1/2<- 1/2)= hn + IE(HBr+ (1/2)) + G0(HBr+ (1/2),v+) –D0(HBr) - IE(H)-SO(Br*)
G0 (HBr+) = we(v++1/2) – wexe (v++1/2)2+weye (v++1/2)3
-(we(1/2) – wexe (1/2)2+weye (1/2)3)

46. HBr, E(0):
H+ +
Br(3/2)
H+ +
Br(1/2)
H+ + Br (3/2)/Br*(1/2)
<- HBr+(3/2,v+)/HBr+*(1/2,v+)
KER/eV
Negligible shift of peaks

47. <- HBr+(3/2,v+)/HBr+*(1/2,v+)
HBr, E(0), J´=1:
H+ +
Br(3/2)
H+ + Br (3/2)/Br*(1/2)
H+ +
Br(1/2)
<- HBr+(3/2,v+)/HBr+*(1/2,v+)
Br/Br* HBr+/HBr+*
½ <- ½
3/2 <- ½
½ <- 3/2
3/2 <- 3/2
v+=
v+=
v+=
v+=
KER/eV
Agust,lab top,C:/…/E0-KER a.pxp

48. H+ + Br-
….via HBr***/H+Br- (2+1) hn
….via HBr+(v+) (2+2) hn
….via H* + Br/Br* (2+2) hn
H+ + Br (3/2)/Br*(1/2)
H+ + Br(3/2,1/2)
H+ + Br*(1/2, 3/2)
V/Ion-pair Ry
Signal of Channel via Ion-pair Signal of Channel via Rydberg
vs. J´ measure of Rydberg-Ion-pair interactions vs. J´

49. <- HBr+(3/2,v+)/HBr+*(1/2,v+)
HBr, E(0):
H+ +
Br(3/2)
H+ + Br (3/2)/Br*(1/2)
H+ +
Br(1/2)
<- HBr+(3/2,v+)/HBr+*(1/2,v+)
Br/Br* HBr+/HBr+*
½ <- ½
3/2 <- ½
½ <- 3/2
3/2 <- 3/2
v+=
v+=
v+=
v+=
KER/eV
Agust,lab top,C:/…/E0-KER b.pxp (Gr1, Lay0)

50. H+ + Br*(1/2, 3/2)<- H* + Br/Br*J´
Agust,lab top,C:/…/E0-KER c.pxp (Gr1, Lay0)

51. H+ + Br (3/2)/Br*(1/2)<- HBr+(v+)
H+ + Br(3/2,1/2)<- H* + Br/Br* J´
Agust,lab top,C:/…/E0-KER c.pxp (Gr1, Lay0)

52. Ion-pair states
V(m+4) and V(m+5) spectra:

53. <- HBr+(3/2,v+)/HBr+*(1/2,v+)
J´= 1
H+ +
Br(3/2)
H+ +
Br(1/2)
H+ + Br (3/2)/Br*(1/2)
<- HBr+(3/2,v+)/HBr+*(1/2,v+)
V(m+5)
Br/Br* HBr+/HBr+*
½ <- ½
3/2 <- ½
½ <- 3/2
3/2 <- 3/2
v+=
v+=
E(0)
V(m+4)
KER/eV
Agust,lab top,C:/…/E0-KER pxp (Gr2, Lay3)

54. H+ + Br*(1/2, 3/2)<- H* + Br/Br*
V(m+5)
J´=
V(m+4)
J´=
E(0)
J´=
2hn/cm-1
Agust,lab top,C:/…/E0-KER d.pxp (Gr3, Lay3)

55. H+ + Br*(1/2, 3/2)<- H* + Br/Br*
Larger for the V states than E(0)
H+ + Br(3/2,1/2)<- H* + Br/Br*

56. H+ + Br*(1/2, 3/2)<- H* + Br/Br*
V(m+5)
J´=
V(m+4)
J´=
E(0)
J´=
2hn/cm-1
Agust,lab top,C:/…/E0-KER d.pxp (Gr3, Lay3)

57. H+ angular distributions:

58. H++Br(3/2)
H++Br(1/2)
H++Br(1/2) || || || (^)
H++Br(3/2) ^ ^ ^
H++Br(1/2) ^ ^ ^
H++Br(3/2) ^ , || ^ , || ^ , ||

59. H++Br(3/2)
H++Br(1/2)
H++Br(1/2) ^ ^ ^
H++Br(3/2) ^ , || || || J´ 1 2 3 4 5 6 7 8 9
H++Br(1/2) ||
||, ^ ^
H++Br(3/2)
^,||

60. H+ + Br(3/2)
[22P] 1S0,3P0
[ B2S ]..
H* + Br*(1/2)
H* + Br (3/2)
H+ + Br-
[ 4P,5s ] 3P0
H + Br**(5s)
V/1S+
E1S+

61. H+ + Br*(1/2)
[22P] 1S0,3P0
[ B2S ]..
H* + Br*(1/2)
H* + Br (3/2)
H+ + Br-
H + Br**(5s)
[ 4P,5s ] 3P0
V/1S+
E1S+

62. Br+ images
HBr Molecular resonances
Br atom resonances

63. HBr Molecular resonances
H + X+ + e J+ v+
HX+ + e
3hn: X+ <- H + X**
2hn: X+ <-<-<- H+ Br/Br*
1hn: X+ <-<-<- H+ Br/Br*
KER´s
H + X** J´ v´
HX**
v´,J´
H+X- /Ion-pair/V
H + Br/Br* HX
J´´
v´´= 0
r(HX)

64. HBr, E(0); Br+ KER´s 1hn 2hn 3hn „blob“! Max: KER(81Br) eV 0,035197
0,03524
0,035307
0,035396
0,035509
0,035644
0,035801
0,03598
0,036177
0,036403
81Br KER
KER(Br(3/2))
KER(Br(1/2)) eV 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0,
81Br KER
KER(Br(3/2))
KER(Br(1/2)) eV 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, 0, J´ 1 2 3 4 5 6 7 8 9 10
„blob“!

65. Br atom resonances E
X+ + e
X**
X/X*
Only
„1hn channel“
observed
H + X+ + e J+ v+
HX+ + e
H + X** J´ v´
HX**
v´,J´
H+X- /Ion-pair/V
H + X/X* HX
J´´
v´´= 0
r(HX)

66. HBr „near-resonance“ interactions:
Exp. 3 & 4 (?):

67. Alternative HBr experiments(3 & 4):
3) „near-resonance“ interaction: k3P1(v´= 0) (k(0)) and V(m+9) for J´= 7
Ref: :

68. 3) „near-resonance“ interaction: k3P1(v´= 0) (k(0)) and V(m+9) for J´= 7
Ref: :

69. 4) „near-resonance“ interaction: 6pp3S-(v´= 0) and V(m+17) for J´= 7,8,9
Ref: :
O Q S

70. 4) „near-resonance“ interaction: 6pp3S-(v´= 0) and V(m+17) for J´= 7,8,9
Ref: :

71. 4) „near-resonance“ interaction: 6pp3S-(v´= 0) and V(m+17) for J´= 7,8,9
Ref: :

72. 4) „near-resonance“ interaction: 6pp3S-(v´= 0) and V(m+17) for J´= 7,8,9
Ref: :