1. HBr The 85466 cm-1 system (slides 2-16)
The cm-1 system (slides 18 –yy)

2. cm-1
4s24p4(3P1)6p, 4D°(1/2)<-<- 2P1/2
H79Br+
79Br+ H+
H81Br+
81Br+

3. Br atomic line: http://www.nist.gov/pml/data/asd.cfm: exp. waven:
cm-1
1.5
0.5
levels:

4. Quite high I(Br+)/I(HBr+) ratio => could be an W = 0 state / E, H, g or V?
Could it be
E(5p,v´=4)
E(6p, v´=0); check quantum defect
H(5d,v´=3)
V(m+18).....unlikely since the intensity is very high(?) ?
What is the B´ assuming J´min = 0 and Q branch?

5. Br atomic line: 2P1/2 H79Br+ 79Br+ H+ H81Br+ 81Br+ = 88847.89-3685.24 =
H79Br+
79Br+ H+
H81Br+
81Br+

6. Br atomic line: 2P1/2 H79Br+ 79Br+ H+ H81Br+ 81Br+ = 88958.04-3685.24
H79Br+
79Br+ H+
H81Br+
81Br+

7. Br atomic line:
2P3/2

8. Br atomic lines: 2P3/2 2P3/2 Ath Br atomic lines(?) ? H79Br+ 79Br+ H+
2P3/2
Ath Br atomic lines(?) ?
H79Br+
79Br+ H+
H81Br+
81Br+

9. greatest perturbation effect is due to a higher lying :
The “IR” suggests that
greatest perturbation effect
is due to a higher lying
V(m+?) state, most probably
V(m+18) or V(m+19)(?):
V(m+18/19)
New
state
V(m+17/18)
ERGO: we ought to be able
to see V(m+18/19) to slightly
higher energy(?); see more
below(slides 14-15)
Most probably W = 0 state

10. 1) Let´s check the criteria:
Could it be
- E(6p, v´=0); check quantum defect
Energetics for HBr: :
HBr, new state at 85466:
Tables:
quantum defect calculations.
IE(HBr )
cm-1
n0(n=6; New state)=
n0(E(n=5,v´=0)=
according to C&G:
RH=
m-1
NEW STATE (assuming n=6): n= 6 ?
n*=n-d
d=n-n*=
n0(n=5)=
predicted position of n=5 band => the closes W=0 Rydberg state which fit this is E(0)!
find d from E(n=5, v´=0):
E(n=5,v´=0): 5
Ergo: d (new state) = 2.45
d(E(n=5,v´=0) = 2.40
Therefore very likely that the
New state =E(n=6,v´=0)

11. 1) Let´s check the criteria::
Could it be
-E(5p,v´=4)
HBr, could new state be E(n=5,v´=4)?
v´=
n0(E)
unit DE
C&G
cm-1 1
2229.3 2
2107.1 3
1973.7
new DE
Far too low!
v´+1
Not likely!

12. 1) Let´s check the criteria:
Could it be
-H(5d,v´=3) :
HBr: could "new state" be H(n=5,v´=3)?
v´=
n0(E)
unit DE
C&G
cm-1 1
2253.7 2
2142.9
new(4?):
Far too small => NO!

13. 1) Let´s check the criteria:
Could it be
-H(6d,v´=0) :
d = 2.25 for H vs
d= 2.45 for New state
Impossible!
ERGO: all in all based on tests in slides 10 – 13 the most likely assignment
for “New state” is E(n=6, v´=0)

14. https://notendur. hi. is/agust/rannsoknir/rempi/hbr/Jan12/XLS-270312ak:
HBr: New state vs Ion-pair states:
E/n0/cm-1
ref. DE
V(m+19)
132.35
370.4
571.1
New state):
ours
238.05
V(m+18)
85228
200.7
guess
V(m+17)
C&G
395.5
V(m+16)
V(m+15)
ours:
V(m+14) ?
V(m-13)
496.9
V(m+12)

15. V(m+18/19) Possible explanation New state V(m+18)???guess 85598.4 cm-1
238.05
370. cm-1
?85228
V(m+18)???guess
cm-1
this could be
V(m+18/19)?
571.1cm-1
200.7
V(m+17
(C&G)
H79Br+
79Br+
H81Br+
81Br+

16. If this is correct V(m+18) ought to be seen for example close to
85228 cm-1 (??)
Could this be V(m+18)? OR
On second thought and after discussing with Long, the H+ signals more probably are
Due to HCl impurity, since no HBr+ and Br+ signals are seen

17. ....in which case the assignment in terms of the V states is more probably as:
V(m+18)
New
state
V(m+17)

18. cm-1
H79Br+
79Br+ H+
H81Br+
81Br+

19. The comparable d values suggests that the 85829.63 cm-1 state :
The cm-1 state: n= 6
n*=n-d=
d=n-n*=
i(n=5, 3D3(v´=0)): 5
i(n=5,3D2(v´=0)):
The comparable d values
suggests that the cm-1 state
is an i3D (n = 6, v´= 0) state
i3D2(n=5) is a lot more intense spectrum
Than the i3D3(n=5) spectrum (see next
Slide) suggesting
that the same should hold for i3D2 (n=6)
Compared to i3D3 (n=6)
-further suggesting that the
cm-1 state
is the i3D2 (n = 6, v´= 0) state
Now let´s compare the i(n=5,v´=0) and i(n=6,v´=0) spectra:

21. i(n=5,v´=0) H79Br+ 79Br+ H+ H81Br+ 81Br+

22. i(n=5,v´=0)

23. i(n=6,v´=0): 85829.63 cm-1 H79Br+ 79Br+ Is this HCl impurity? H+

24. Long, please fit data for i(n=6,v´=0) spectrum to derive B´, D´, etc.!
Comments:
Long, please fit data for i(n=6,v´=0) spectrum to derive B´, D´, etc.!
, , from Long:
This state’s parameters(J’ starts at 2):
            Te        =85833±0.517
            Bv       =7.835 ±0.0521
            Dv       = ±
We will now need analysis of the I(Br+)/I(HBr+) vs J´ ratios for the
E(n=6,v´=0) state assuming
-Large contribution from V(m+18) interaction
-Small contribution from V(m+17) interaction

25. Content for “HBr-New states paper” for JMS(?):
Previously observed Rydberg states in 1hv experiments, but unobserved states
in 2hv / REMPI:
-k3P0 (-> same as in HBr Fvs V paper (overlap))
-k3P1..analysis rechecking needed, perturbation for J´=4 needs to be interpreted.
-m3P2(2)..analysis needed to derive B´and D´.
II. Previously unobserved and unanalysed states:
E(n=6,v´=0)...IR analysis needed.
i(3D2)(n=6,v´=0)..B´,D´analysis needed. :
III. V / ion-pair states:
Previously unanalysed
Previously unobserved
m-1, m+4, m+6, m+9, m+11, m+15, m+18
...B´, D´ analysis needed.

26. Summary of observations for V(m+i) states:
C&G Obs. (rot. Param)
Kvaran etal., 1998 REMPI-current Obs. (rot. Param)
NOW (REMPI-TOF) Obs. (rot. Param)
m-1 X
m+0
m+1
X(0)
m+2
m+3
X(X) x
m+4
m+5
m+6
m+7
m+8
m+9
m+10
m+11
m+12

27. Summary of observations for V(m+i) states:
C&G Obs. (rot. Param)
Kvaran etal., 1998 REMPI-current Obs. (rot. Param)
NOW (REMPI-TOF) Obs. (rot. Param)
m+13
X(X) x
m+14
m+15
m+16
m+17
X(0) X
m+18
m+19
m+20
m+21
m+22

28. Fig 1b
Fig 1a
m+17
m-1
m+18
m+12 k0 k1 m2 E6 i6

29. DE(J´,J´-1) E(n=6,v´=0) state J´