Off-resonance interaction between E and V state of HCl and HBr Jingming Long 22/09/2011

Near-resonance interaction Off-resonance interaction Heterogeneous (  >0)Homogeneous (  =0) Rydberg and ion-pair interaction V1+V1+ E1+E1+ j3-j3- f3f3 E1+E1+ …

H*+X or H+X* H + +X - Rydberg state Ion pair state From ground state H+X * HX * H*+X HX* * X+X+ H+H+ HX + X+X+ H+H <  <10  ~0  ~1

Linewidth: Relative signal Intensity ratio:

Kristján Matthíasson, Jingming Long, Huasheng Wang, and Ágúst Kvaran. “Two-dimensional resonance enhanced multiphoton ionization of H i Cl:i = 35, 37: State interactions, photofragmentations and energetics of high energy Rydberg states”[J], J.Chem.Phys. (2011) Near-resonance interaction Homogeneous perturbation

H 35 ClH 37 Cl

Near-resonance interaction heterogeneous perturbation Ágúst Kvaran, Kristján Matthiasson, and Huasheng Wang. “Two- dimensional „2+n… resonance enhanced multiphoton ionization of HCl:State interactions and photorupture channels via low- energy triplet Rydberg states”[J]. J.Chem.Phys (2009)

HCl E 1  + (v’=1) V 1  + (v’=15) V 1  + (v’=14) V 1  + (v’=10) E 1  + (v’=0) V 1  + (v’=11) Off-resonance interaction Homogeneous perturbation

H 35 Cl + 35 Cl + H 37 Cl + 37 Cl + H+H+

 E(E0-V10)  E(V11-E0) W 10 : 172cm -1 W 11 :160cm -1  : 0.6 c 2 =1/2

E 1  + (v’=1) W 14 : 123cm -1 W 15 :120cm -1  : 1.4 c 2 =1/2  : 0

HBr E 1  + (v’=1) V 1  + (v’=m+9) V 1  + (v’=m+8) V 1  + (v’=m+4) E 1  + (v’=0) V 1  + (v’=m+5) Off-resonance interaction Homogeneous perturbation

E 1  + (v’=0)

* Calculation J’  E(0-m+4)  E(0-m+5) * * *

E 1  + (v’=0) W 1,m+4 : 31cm -1 W 1,m+5 : 45cm -1  : 1.8  : 0.026

Comparison of the linewidth between experiment and calculation E 1  + (v’=0)

W 1,m+8 : 53cm -1 W 1,m+9 : 58cm -1  : 8.4  : 0.03 E 1  + (v’=1)

HClHBr E 1  + (v’=0) Intensity ratios for low J’ are flat. Calculation is not good agree with experiment. Linewidths are more broadening than HCl which have the same trend as intensity ratios. Calculation is good agree with experiment. E 1  + (v’=1) Intensity ratios for low J’ are flat. Calculation is good agree with experiment. Linewidths broadening can’t be explained at present. Suposed it’s due to predissociation and tunneling. Calculation is good agree with experiment. Summary

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