Perturbation analysis in REMPI Spectra of HCl and HBr 01/03/2011 Jingming Long Due to new assignment for g3S-(2-0) Slide 20, 21, 23, 26, 27 are modified

3 3 2 2 1 J=0 1 J=0 Ion pair state Rydberg state G.Herzberg, Molecular Spectra and Molecular Structure I - Spectra of Diatomic Molecules(1950)

HX+ HX+ X+ H+ X+ H+ HX** H*+X or H+X* H*+X H+X* H++X- HX* Ion pair state Rydberg state From ground state

10-1<a<10 g ~0 d ~1 Agust kvaran, Kristan Matthiasson, and Huasheng Wang. J.Chem.Phys.131,044324(2009)

HCl V1S+(0+)(9,0) g3S-(0+)(0,0) V1S+(0+)(10,0) V1S+(0+)(14,0) E1S+(0+)(1,0) V1S+(0+)(15,0) V1S+(0+)(20,0) j3S-(0+)(0,0) V1S+(0+)(21,0)

The interaction between g3S-(0+)(0,0) and V1S-(0+)(9,0)(10,0) Exp Calc V v’=9 V v’=10 a=0.29 g=0 W9=123cm-1 W10=110cm-1

The interaction between E1S+(0+)(1,0) and V1S-(0+)(14,0)(15,0) g=0 W14=123 cm-1 W15=145cm-1

The interaction between j3S-(0+)(0,0) and V1S-(0+)(20,0)(21,0) V v’=20 Exp Calc V v’=21 a=2.1 g=0.0319 W20=25 cm-1 W21=25cm-1

The interaction between j3S-(0+)(0,0) and V1S-(0+)(20,0)(21,0) Calc Exp V v’=20 V v’=21 a=4 g=0.0131 W20=25cm-1 W21=25cm-1

Robert Callaghan and Robert J.Gordon, J.Chem.Phys.93(7) , October 1990 HBr E1S-(0+)(0,0) V1S+(0+)(m+4) V1S+(0+)(m+8) E1S+(0+)(1,0) , g3S-(0+)(2,0) V1S+(0+)(m+9) Robert Callaghan and Robert J.Gordon, J.Chem.Phys.93(7) , October 1990

V v’=m+4 E(0)

Corrected g3S-(2-0)

DE(g2-E1)) DE(V(m+9)-E1) DE(E1-V(m+8)) DE(g2-V(m+8)) DE(V(m+9)-g2) J 219.0174 471 136 355.6 251.4 1 222.2350247 466.59636 140.12612 362.7373 243.985204 2 228.4676225 457.16604 148.62508 377.2543 228.536836 3 237.3098899 441.46296 161.99032 400.0359 203.417344 4 248.153872 417.618 180.962 429.6096 168.9704 5 260.188962 383.139 206.527 467.3451 122.3209 6 272.4019015 334.91076 239.91892 508.8547 65.974964 7 283.5767805 269.19504 282.61808 570.3932 -18.580064 8 292.2950371 181.63056 336.35152 628.6466 -110.664477 9 296.935458 67.233 403.093 700.0285 -229.702458 10 295.674178 -79.605 485.063 780.7372 -375.279178

The interaction between E1S-(0+)(1,0) and V1S-(0+)(m+8)(m+9) Exp V v’=m+8 Calc V v’=m+9 a=8.4 g=0.03 WV(m+8)=53 WV(m+9)=58

79Br H79Br

The interaction between g3S-(0+)(2,0) and V1S-(0+)(m+8)(m+9) Exp Calc V v’=m+8 V v’=m+9 a=1.44 g=0.02 WV(m+8)=9.29 WV(m+9)=9.29

79Br/H79Br 81Br/H81Br 79Br H79Br

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