1. 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

2. 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)

3. 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

4. 10-1<a<10
g ~0
d ~1
Agust kvaran, Kristan Matthiasson, and Huasheng Wang. J.Chem.Phys.131,044324(2009)

5. 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)

7. 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

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

11. 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

12. 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

13. 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

17. V v’=m+4
E(0)

21. Corrected
g3S-(2-0)

23. DE(g2-E1)) DE(V(m+9)-E1) DE(E1-V(m+8)) DE(g2-V(m+8)) DE(V(m+9)-g2) J
471
136
355.6
251.4 1 2 3 4 5 6 7 8 9
67.233 10

24. 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

25. 79Br
H79Br

26. 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

27. 79Br/H79Br
81Br/H81Br
79Br
H79Br

28. Thank you