Post on 20-Jan-2016
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+E1+
j3- f3
E1+ …
H*+X or H+X*
H++X-
Rydberg state
Ion pair state
From ground state
H+X*
HX*
H*+X
HX**X+ H+
HX+
2
1X+ H+HX+
12
02
01 21
cca 0
10
2 21 ccb
222
21 1
)( ccHXI
211
22 2
)( ccXI
BrClX ,
0
1 0
2
1
2
2
1
1
21
10-1<<10 ~0 ~1
||2
||4)(
2
1 212
22
2,1 E
WEci
12
221 cc
)1(
))1((
)(
)(2
22
2c
c
HXI
XI
})1(
)]1([
)1(
)]1([{
)(
)(2,0
2,0
2,0
2,0
j
j
i
i
c
c
c
c
HXI
XI
)}||4()||4{(* 2,0
2,0,0
2,0
2,0,0
~
jjjiii WEEWEEE
Linewidth:
Relative signal Intensity ratio:
Kristján Matthíasson, Jingming Long, Huasheng Wang, and Ágúst Kvaran. “Two-dimensional resonance enhanced multiphoton ionization of HiCl:i = 35, 37: State interactions, photofragmentations and energetics of high energy Rydberg states”[J], J.Chem.Phys. (2011)
Near-resonance interactionHomogeneous perturbation
H35Cl H37Cl
Near-resonance interactionheterogeneous 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.131.044324(2009)
HCl
E1+(v’=1)
V1+(v’=15)
V1+(v’=14)
V1+(v’=10)
E1+(v’=0)
V1+(v’=11)
Off-resonance interactionHomogeneous perturbation
400x103
300
200
100
0
Rel
ativ
e In
tens
ity a
.u.
84.2x10384.083.883.683.483.2
Wavenumber /cm-1
Q
V1
v'=10) V
1
v'=11)
Q02468 2 046810
E1
v'=0)
0246810Q
S
O
H35Cl+
35Cl+
H37Cl+
37Cl+
H+
E(E0-V10) E(V11-E0)345.9382 424.22353
348.88047 420.06753353.73699 414.56881
363.2478 404.11409 388.52561 369.807 352.7285 339.09694
W10: 172cm-1 W11 :160cm-1
: 0.6
0.7
0.6
0.5
0.4
0.3
0.2
0.1
0.0
I(35
Cl+
)/I(
H35
Cl+
)
0 1 2 3 4 6 7 8J'
Experiment Calculation
c2=1/2
3x106
2
1
0
-1
-2
Rel
ativ
e In
ten
sity
86.4x10386.286.085.885.6
Wavenumber 2hv/cm-1
86.0085.9585.9085.8585.80
x103
35Cl+
H35Cl+
Q
QQ 05
0
0
2468
V1
E1
V1
86.6x103
86.4
86.2
86.0
85.8
En
erg
y /
cm
-1
V1
'=14)
V1
'=15)
E1
'=1)
J '=0123
4
5
J '=01234
5
6
7
J '=0123456
E1+(v’=1)
W14 : 123cm-1 W15 :120cm-1
: 1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
I(35
Cl+
)/I(
H35
Cl+
)
0 1 2 3 4 5J'
1.2
1.0
0.8
0.6
0.4
0.2
0.0
Experiment From V(v'=14) From V(v'=15)
c2=1/2
: 0
HBr
E1+(v’=1)
V1+(v’=m+9)
V1+(v’=m+8)
V1+(v’=m+4)
E1+(v’=0)
V1+(v’=m+5)
Off-resonance interactionHomogeneous perturbation
300x103
200
100
0
-100
-200
Re
lati
ve
Inte
ns
ity
77.98x10377.9677.9477.9277.9077.8877.86
Wavenumber 2hv/cm-1
Q
02489 7 6
E1
79Br
H79
Br
10
300x103
250
200
150
100
Rel
ativ
e In
ten
sity
77.85x10377.8077.7577.7077.6577.6077.55
Wavenumber 2hv /cm-1
0
Q
12345678
V1m+4)
E10-0) O
79Br
H79
Br
400x103
300
200
100
0
Rel
ati
ve
Inte
ns
ity
77.98x10377.9677.9477.9277.9077.8877.86
Wavenumber 2hv/cm-1
H+
79Br
+
H79
Br+
81Br
+
H81
Br+
E1+(v’=0)
79.8x103
79.6
79.4
79.2
Ener
gy L
evel
E1
V1
m+5)
V1
m+4)
J'=012
3
4
5
6
7
8
9
J'=02
4
5
6
7
8
9
J'=02
4
6
5
3
*Calculation
J’ E(0-m+4) E(0-m+5)
0 110.8 447.81 119.3 441.22 133.4 425.43 155.1 405.6
4 184.6 375.009
5 219.3 333.52
6 266 302.249
7 322.3 266*8 379 235*9 438.8 200*
E1+(v’=0)
W1,m+4: 31cm-1 W1,m+5: 45cm-1: 1.8 : 0.026
0.30
0.25
0.20
0.15
0.10
0.05
0.00
I(79
Br+
)/I(
H79
Br+
)
1 2 3 4 5 6 7 8 9J'
0.30
0.25
0.20
0.15
0.10
0.05
0.00
Experiment From V(v'=m+4) From V(v'=m+5)
Comparison of the linewidth between experiment and calculation
1.2
1.0
0.8
0.6
0.4
0.2
0.0
Lin
ewid
th
/cm
-1
1 2 3 4 5 6 7 8 9J'
1.2
1.0
0.8
0.6
0.4
0.2
0.0
Experiment From V(v'=m+4) From V(v'=m+5)
E1+(v’=0)
600x103
400
200
0
Rel
atvi
e In
tens
ity
80.2x10380.180.079.9
Wavenumber 2hv/cm-1
Q0123456
E1
79Br
H79
Br
V1
(v'=m+8)
Q01234567
2.5
2.0
1.5
1.0
0.5
0.0
I(79
Br+
)/I(H
79Br+
)
0 1 2 3 4 5 6 7J '
2.5
2.0
1.5
1.0
0.5
0.0
Experiment From V(v'=m+8) From V(v'=m+9)
W1,m+8: 53cm-1 W1,m+9: 58cm-1
: 8.4 : 0.03
E1+(v’=1)
HCl HBr
E1+(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.
E1+(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
Thank you