HI

Relevant to the HI- Perturb.II paper: pages:

H(2) ion intensities (system (b))……………………… 2-9

https://notendur.hi.is/~agust/rannsoknir/rempi/hi/July14/PPT-141219.pptx https://notendur.hi.is/~agust/rannsoknir/rempi/hi/July14/PXP-141219.pxp https://notendur.hi.is/~agust/rannsoknir/rempi/hi/July14/XLS-141219.xlsx

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86420 J´

I(M+)/Itotal Itotal = I(H+)+I(I+)+I(HI+) H(2), system (b)

I(I+)

I(H+)

I(HI+)

https://notendur.hi.is/~agust/rannsoknir/rempi/hi/PXP-141219.pxp; Lay: 0, Gr:0

2.5

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86420

I(H+)/I(HI+) H(2), system (b)

https://notendur.hi.is/~agust/rannsoknir/rempi/hi/PXP-141219.pxp; Lay: 2, Gr:2

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x106

86420

I(M+) H(2), system (b)

I(I+)

I(H+)

I(HI+)

J´

https://notendur.hi.is/~agust/rannsoknir/rempi/hi/PXP-141219.pxp; Lay: 1, Gr:1

Comments:

• Slide 2: graphs for I+ and H+ are close to mirror images, meaning that as I+ increases, H+ decreases and vice versa. This suggests that, considering the two ionformation channel a) I+ and b)H+, only, these are „competing in nature“, in the sense that as (a) increases (b) decreases and vice versa.

• Slide 2: There is some correlation between the graphs for H+ and HI+ : thus, both graphs show enhancements for J´= 3. Considering that the H+ formation occurby the two (three) major channels:b-1) HI** +hv -> H* + Br/Br* followed by H* + hv -> H+ + e- andb-2) HI** + hv -> HI# -> HI+ + e- followed by HI+ + hv -> H+ + I-one of which (b-2) involves H+ formation after HI+ formation:If H+ was solely formed by channel (b-2) and by assuming that H +, formed from HI+, is independent of J´ I(H +) = C*I(HI+); C = constant holds (first approximation) =>i.e. I(H+)/I(HI+) = C. The fact that that is not the case (see slide 3) whereas there is some correlation between the graphs for H+ and HI+ suggest that both channels ((b-1) and (b-2)) are involved.

• In conclusion:

HI+ (b-2) H* I*

H+ (b-2)

(a)(b-2) (b-1)

H+ (b-1)

i.e.

Itotal = I(H+(b-1)) + I(H+ (b-2)) + I(HI+ (b-2)) + I(I+ (a))

I+ (a)

(b)

2hv

HI**(mixed)

(a), (b), hence (b)/(a) are J´-dependent; ERGO let´s check:

Assuming that I(H+) + I(HI+) is proportional to the rate of (b); I(H+) + I(HI+) = c1*(b) I(I+) is proportional to the rate of (a); I(I+) = c2*(a)

(I(H+) + I(HI+) )/I(I+) = (c1/c2) (b)/(a) = C1*(b)/(a)

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86420 J´

https://notendur.hi.is/~agust/rannsoknir/rempi/hi/PXP-141219.pxp; Lay: 3, Gr:4

(I(H+) + I(HI+) )/I(I+)

Particularely large enhancement of channel (b) over (a) for J´= 3 but ca.independent or slightly decreasing with J´ other J´s

Now let´s check W = 1 predissociation criterias.

Reviewer for our JCP paper 2013 (HCl and HBr, E vs V states) said:

the SO matrix element between C1Π andt3Σ+ with dominant configurations differing by 2 spin-orbitals would be very weak. The<E1Σ+|J+L−|C1Π > matrix element is also very weak because the Rydberg orbital ofE is 4pπ while the Rydberg orbital of C is 4sσ. On the contrary, there is a possibleJ+L− coupling between E1Σ+ and D1Π which is 4pσ: these two states correspond to a”p complex”.