1. Agust,www,....january09/PPT-120309aka.ppt Agust,heima,... january09/XLS-120309ak.xls About enhanced I( 35 Cl + )/I(H 35 Cl + ) values in a) g 3  + (1),v´=0 & b) for f 3  (3), v´=0 (2+n) REMPI spectra In terms of the “gateway mechanism”

2. 3+3+ SO coupling; SO coupling; see Table 2 in http://www3.hi.is/~agust/rannsoknir/rempi/hcl/january09/PPT-260209ak.ppt Example for gateway mechanism: g 3  + (1) v´=0 C 1  ; b 3  1); g 3  - (1) 1) 2) H + Cl* / H + Cl  E = 880cm-1 ( AK PhD Thesis (page 9-10, fig. 1.3) 2xh 3xh Cl** Cl + 3)

3. The following deals with process 3), i.e. H + Cl** H + Cl* H + Cl See next slides

4. Agust,heima,..january09/PXP-120309ak.pxp (1)(2) (3)(4) 4p 4 P o 1/2 4p 4 P o 3/2 4p 4 P o 5/2 (1)From H + Cl 82518.5 / (2+n)REMPI for g 3  + (1),v´=0, J´= 3 (2)From H + Cl* 82518.5 / (2+n)REMPI for g 3  + (1), v´=0, J´= 3 (3)From H + Cl 81784.9 / (2+n)REMPI for f 3  (3), v´=0, J´= 6 (4)From H + Cl* 81784.9 / (2+n)REMPI for f 3  (3), v´=0, J´= 6 H + Cl**

5. 4p 4 P o 1/2 4p 4 P o 3/2 4p 4 P o 5/2 83399.4 83360.55 Difference = 38.85 (2) From H + Cl* 82518.5 / (2+n)REMPI for g 3  + (1), J´= 3 Agust,heima,..january09/PXP-120309ak.pxp This corresponds to a “highly allowed” 2xh resonance transition Cl*(3p, 2 P o 1/2 ) ->-> Cl**(4p, 4 P o 1/2 ), i.e.:  L=0;  J=0,  l=0(p->->p), odd->->odd whereas  S = 2 ! Closer look:

6. Hence, the enhanced I( 35 Cl + )/I(H 35 Cl + ) value for g 3  + (1),v´=0, J´=3 (see below #) could possible be due to resonance excitation between the H+Cl*(3p, 2 P o 1/2 ) and H + Cl**(4p 4 P o 1/2 ) surfaces after dissociatin via gateway Rydberg state (due to SO couplings) # On the other hand there is no obvious, analogous explanation for enhanced I( 35 Cl + )/I(H 35 Cl + ) value for f 3  (3), v´=0, J´=6,