HBr: F12(v´=1) <-> V(v´=m+7) interaction:W12 determination from line shifts:

agust,heima,...June11/Peaks of F1 and V(m+7) detlta2 for HCl state-141211jlak.xlsagust,www,....June11/PPT-141211aka.pptagust,heima,...June11/PXP-141211ak.pxpagust,heima,...June11/HBr 79040_80120-151211.pxp

E(J´,J´-1)Q

49.0199165.187581.5216198.91389113.056129.7394

J'012345678

E(J´,J´-1)Q

47.7536563.5010579.4166196.29238110.2204126.3927142.0013

J'0123456789

H79Br+ H81Br+

agust,heima,...June11/Peaks of F1 and V(m+7) detlta2 for HCl state-141211jlak.xls

120

100

80

60

876543

140

120

100

80

60

9876543

H79Br+ H81Br+

Clear deviations from linearity

E(J´,J´-1) derived from Qlines of F12

J´ J´agust,heima,...June11/PXP-141211ak.pxp

ERGO: W12 can be derived according to

http://www3.hi.is/~agust/rannsoknir/rempi/hcl/Jan11/PDF-020111ak.pdfAndhttp://www3.hi.is/~agust/rannsoknir/rempi/hcl/Jan11/PPT-190111ak.ppt

120

100

80

60

876543

Coefficient values ± one standard deviation a = 0.60454 ± 0.0266 b = 16.142 ± 0.00488

H79Br+

agust,heima,...June11/PXP-141211ak.pxp

140

120

100

80

60

9876543

Coefficient values ± one standard deviation a = 0.6369 ± 0.0704 b = 15.713 ± 0.0108

agust,heima,...June11/PXP-141211ak.pxp

35

30

25

20

15

10

4.03.53.02.52.01.51.0

agust,heima,...June11/PXP-141211ak.pxp; lay:2; Gr:4

V(v´=m+7)DE(J´,J´-1)79Br+

8.3177917.027227.419936.0875

J´

1234

VDE81Br+

7.9951616.182426.253634.901

70

60

50

40

30

20

10

8642

agust,heima,...June11/PXP-141211ak.pxp; lay:3; Gr:3

V(v´=m+7)DE(J´,J´-1)H+Use B´´and D´´ for i =79

V(v´=m+7)DE(J´,J´-1)H+Use B´´and D´´ for i =81

Lets have a look at the H+ REMPI spectrum:

20

10

0

-10

-20

x103

79.4579.4079.3579.3079.2579.20x10

3

F1 (v'=1)

QP R S2

4

68 2 3 4 5 62 3 542

Move J´=5 peak from + to +

agust,heima,...June11/HBr 79040_80120-151211.pxp; Lay:0 ; Gr:2

i=79i=81

6

5

4

3

6

5

4

7

This is closer to what one might expect, i.e. a drop in E(6,5):

agust,heima,...June11/Peaks of F1 and V(m+7) detlta2 for HCl state-141211jlak.xls

J´

F(v´=1)V(v´=m+7)

E(J´,J´-1)

J´

J´

Ca. 25 cm-1 drop!

20

10

0

-10

-20

x103

79.4579.4079.3579.3079.2579.20x10

3

F1 (v'=1)

QP R S2

4

68 2 3 4 5 62 3 542

Lets have a look at the H+ REMPI spectrum:

Move J´=5 peak from + to +

H+

J' Q0 79482.51 79473.72 79456.63 79432.84 79401.55 793586 79283.227 79219.28 79145.39 79065.6

agust,heima,...June11/HBr 79040_80120-151211.pxp; Lay:0 ; Gr:2

i=79i=81 H+

J' Q0 79482.51 79473.72 79456.63 79432.84 79401.55 793586 79283.227 79219.28 79145.39 79065.6

i.e. line positions:

agust,heima,...June11/Peaks of F1 and V(m+7) detlta2 for HCl state-141211jlak.xls

agust,heima,...June11/Peaks of F1 and V(m+7) detlta2 for HCl state-141211jlak.xls

J´

  F1D2                  H79Br+ E DE DE0 E0 D(E-E0) EV(J´) EV0 W12J' Q Q Q Q Q Q Q    

0            79482.5   1            79490.82   2 79310.7 79362.05    79362.05 0 79507.95 79507.95 3 79308.4 79411.06 49.01991 49.03054 79411.08 0.010631 79535.46 79535.45 4 79305.2 79476.25 65.1875 65.17254 79476.25 0.004325 79572.55 79572.55 5 79301.3 79557.77 81.52161 81.31454 79557.56 0.211395 79614.47 79614.26 6 79297.8 79656.69 98.91389 97.45654 79655.02 1.66874 79642.1 79643.77 4.6426167 79291.5 79769.74 113.056 113.5985 79768.62 1.126153 79697.44 79698.578 79285 79899.48 129.7394 129.7405 79898.36 1.125058 79759.78 79760.91

              79833.14     H81Br+   DE            J' Q   Q            

0            79482.5   1            79490.4   2 79310.4 79360.48    79360.48 0 79506.68 79506.68 3 79308.1 79408.23 47.75365 47.7759 79408.25 0.022255 79532.93 79532.91 4 79304.9 79471.73 63.50105 63.4889 79471.74 0.010107 79568.33 79568.32 5 79301 79551.15 79.41661 79.2019 79550.94 0.204604 79608.15 79607.94 6 79297.4 79647.44 96.29238 94.9149 79645.86 1.58208 79633.26 79634.84 4.4652917 79291.2 79757.66 110.2204 110.6279 79756.49 1.174562 79685.66 79686.848 79284.7 79884.05 126.3927 126.3409 79882.83 1.226332 79744.65 79745.889 79277.4 80026.06 142.0013 142.0539 80024.88 1.173711 79814.26 79815.43 

                                        H+     E   DE      

J' Q Q (original)   Q(81) Q(79)        0 79482.5 79482.5  79482.5 79482.5       1 79473.7 79473.7  79490.4 79490.82 7.895161 8.317794   2 79456.6 79456.6  79506.68 79507.95 16.28236 17.12722   3 79432.8 79432.8  79532.93 79535.46 26.25365 27.51991   4 79401.5 79401.5  79568.33 79572.55 35.40105 37.0875   5 79358 79344.5  79608.15 79614.47 39.81661 41.92161   6 79283.22 79283.22  79633.26 79642.1 25.10738 27.62889   7 79219.2 79219.2  79685.66 79697.44 52.40538 55.34095   8 79145.3 79145.3  79744.65 79759.78 58.99267 62.33944   9 79065.6 79065.6  79814.26 79833.14 69.60128 73.35599