HBr The 85466 cm-1 system (slides 2-16) The 85829.63 cm-1 system (slides 18 –yy) https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/PPT-270312ak.ppt

85466.05 cm-1 4s24p4(3P1)6p, 4D°(1/2)<-<- 2P1/2 85462.445 H79Br+ 79Br+ H+ H81Br+ 81Br+ https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/PXP-270312ak.pxp

Br atomic line: http://www.nist.gov/pml/data/asd.cfm: exp. waven: 85462.445 cm-1 1.5 0.5 3685.24 levels: 89147.685 https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/XLS-270312ak.xls http://www.nist.gov/pml/data/asd.cfm:

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?

Br atomic line: 2P1/2 H79Br+ 79Br+ H+ H81Br+ 81Br+ = 88847.89-3685.24 85162.65 = 88847.89-3685.24 H79Br+ 79Br+ H+ H81Br+ 81Br+ https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/PXP-270312ak.pxp

Br atomic line: 2P1/2 H79Br+ 79Br+ H+ H81Br+ 81Br+ = 88958.04-3685.24 85272.8 H79Br+ 79Br+ H+ H81Br+ 81Br+ https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/PXP-270312ak.pxp

Br atomic line: 2P3/2 85590.8 https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/PXP-270312ak.pxp

Br atomic lines: 2P3/2 2P3/2 Ath Br atomic lines(?) ? H79Br+ 79Br+ H+ 85824.83 2P3/2 Ath Br atomic lines(?) 85767.29 ? H79Br+ 79Br+ H+ H81Br+ 81Br+ https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/PXP-270312ak.pxp

greatest perturbation effect is due to a higher lying https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/Unknown%20state%20at%2085465cm-1.pdf : 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

1) Let´s check the criteria: Could it be - E(6p, v´=0); check quantum defect Energetics for HBr: https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/PPT-180112ak.ppt: https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/XLS-270312ak.xls : HBr, new state at 85466: Tables: quantum defect calculations. IE(HBr ) 94205.52 cm-1 https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/PPT-180112ak.ppt: n0(n=6; New state)= 85466.05 n0(E(n=5,v´=0)= 77939.5 according to C&G: https://notendur.hi.is/agust/rannsoknir/papers/jcp93-4624-90.pdf RH= 10973732 m-1 109737.3 NEW STATE (assuming n=6): n= 6 ? n*=n-d 3.543518 d=n-n*= 2.456482 n0(n=5)= 77243.22 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 2.597386 2.402614 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)

1) Let´s check the criteria: https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/XLS-270312ak.xls : Could it be -E(5p,v´=4) HBr, could new state be E(n=5,v´=4)? v´= n0(E) unit DE C&G 77939.5 cm-1 1 80168.8 2229.3 2 82275.9 2107.1 3 84249.6 1973.7 new 85466.05 1216.45 DE Far too low! v´+1 Not likely! https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/PXP_280312ak.pxp

1) Let´s check the criteria: Could it be -H(5d,v´=3) https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/XLS-270312ak.xls : HBr: could "new state" be H(n=5,v´=3)? v´= n0(E) unit DE C&G 79645.5 cm-1 1 81899.2 2253.7 2 84042.1 2142.9 new(4?): 85466.05 1423.95 Far too small => NO!

1) Let´s check the criteria: Could it be -H(6d,v´=0) https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/XLS-270312ak.xls : 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)

https://notendur. hi. is/agust/rannsoknir/rempi/hbr/Jan12/XLS-270312ak https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/XLS-270312ak.xls : HBr: New state vs Ion-pair states: E/n0/cm-1 ref. DE V(m+19) 85598.4 132.35 370.4 571.1 New state): 85466.05 ours 238.05 V(m+18) 85228 200.7 guess V(m+17) 85027.3 C&G 395.5 V(m+16) 84631.8 284.988 V(m+15) 84346.812 ours: V(m+14) ? https://notendur.hi.is/jil3/work/HBr/Overview%20HBr.pdf V(m-13) 82916.3 496.9 V(m+12) 82419.4

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 85598.4 cm-1 this could be V(m+18/19)? 571.1cm-1 200.7 V(m+17 85027.3 (C&G) H79Br+ 79Br+ H81Br+ 81Br+ https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/PXP-270312ak.pxp

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 https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/PXP-270312ak.pxp

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

85829.63 cm-1 H79Br+ 79Br+ H+ H81Br+ 81Br+

The comparable d values suggests that the 85829.63 cm-1 state https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/XLS-270312ak.xls : The 85829.63 cm-1 state: n= 6 n*=n-d= 3.61961 d=n-n*= 2.38039 i(n=5, 3D3(v´=0)): 5 2.625501 2.374499 i(n=5,3D2(v´=0)): 2.654396 2.345604 The comparable d values suggests that the 85829.63 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 85829.63 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:

https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/PXP_280312aka.pxp

i(n=5,v´=0) H79Br+ 79Br+ H+ H81Br+ 81Br+ https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/PXP_280312aka.pxp

i(n=5,v´=0) https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/PXP_280312aka.pxp

i(n=6,v´=0): 85829.63 cm-1 H79Br+ 79Br+ Is this HCl impurity? H+ https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/PXP_280312aka.pxp

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.! e-mail, 280312, from Long: This state’s parameters(J’ starts at 2):             Te        =85833±0.517             Bv       =7.835 ±0.0521             Dv       =0.00029402±0.00106 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

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.

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

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

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

DE(J´,J´-1) E(n=6,v´=0) state J´ https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/PXP-010512ak.pxp https://notendur.hi.is/agust/rannsoknir/rempi/hbr/Jan12/XLS-010512ak.xls