two-dimensional (2+n) rempi spectroscopy: state interactions, photofragmentations and energetics of...
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TWO-DIMENSIONAL (2+n) REMPI SPECTROSCOPY: STATE INTERACTIONS, PHOTOFRAGMENTATIONS AND ENERGETICS OF THE HYDROGEN HALIDES
JINGMING LONG, HUASHENG WANG, KRISTJÁN MATTHÍASSON,
HELGI RAFN HRÓÐMARSSON, ÁGÚST KVARAN Science Institute, University of Iceland, Dunhaga 3, 107 Reykjavík, Iceland.
Oral presentation at “international Symposium on Molecular Spectroscopy; 66th Meeting”June 20-24, 2011, Ohio State University
Voltagedevider
HV-2Kv
HX nozzle
TurboPump
TOF
lense
MCP detector
oscilloscope
computer
Excimer Laser
In
out
Dye- Laser
SHG
Time delay200-1200 S
laser control
Pellin Broca prism
SHG control
In
out
REMPI = Resonance Enhanced MultiPhoton Ionization
Resonance Excitation to high energy states of neutral species,followed by photon ionization;For example:
1xh
2xh
2
E
AB
AB+ + e
AB**
-28.5
-28.0
-27.5
-27.0
-26.5
-26.0
x103
4003002001000
Intensity
Mw1 3512
H+
35Cl+
H35Cl+
H37Cl+
12C+
Two photon resonance excitation=82842.36 cm-1
Mass spectrum RCl = HCl
80
70
60
50
40
30x1
03
8006004002000
82849.4 cm-1
j´=2
82848.76j´=3
82847.8j´=4
82846.44j´=5
82844.84j´=6
82836.36j´=9
82842.36j´=7
82839.8j´=8
82833.6cm-1
82842.88
Mw / rel.
35Cl+
H35Cl+
H37Cl+
30,0323
32,1132
34,2637
36,484
38,7739
41,1336
43,5629
46,0619
82
83
3,6
82
83
5,6
7
82
83
8,4
24
82
84
0,7
14
29
82
84
2,3
6
82
84
4,1
27
27
82
84
6,2
4
82
84
7,9
92
82
84
9,8
26
67
82
85
1,7
46
67-30000-28500-27000-25500-24000-22500-21000-19500-18000-16500-15000-13500-12000-10500-9000-7500-6000-4500-3000-15000
150030004500600075009000
10500120001350015000
2xhv
Mw
35Cl+
37Cl+H37Cl+
H35Cl+
/cm-1
r(H-X)
Energy
HX
H X ** H+--X-
HX+ H+ X+
e-
e-
+
HX REMPI:
IE limit
v´
J´
v´
J´
r(H-X)
Energy
HX
H X ** H+--X-
HX+ H+ X+
e-
HX+ H+ X+
e-
e-
+
HX REMPI:
IE limit
v´
J´
v´
J´
Rel
ativ
e in
ten
sity
/a
.u.
81.45x103
81.4081.3581.3081.2581.2081.15Wavenumber 2h/cm
-1
I1 Q
2468
P
234567
R
2 3 4 5 6 7 8
S
2 3 4 5 6
H79Br+
r(H-X)
Energy
HX
H X ** H+--X-
HX+ H+ X+
e-
HX+ H+ X+
e-
e-
+
HX REMPI:
IE limit
v´
J´
v´
J´
Rel
ativ
e in
ten
sity
/a
.u.
81.45x103
81.4081.3581.3081.2581.2081.15Wavenumber 2h/cm
-1
I1 Q
2468
P
234567
R
2 3 4 5 6 7 8
S
2 3 4 5 6
H79Br+
Re
lati
ve i
nte
ns
ity
/a
.u.
81.45x103
81.4081.3581.3081.2581.20Wavenumber 2h/cm
-1
I1 Q2468
P234567
R2 3 4 5 6 7 8
S2 3 4 5 6
H79Br+
r(H-X)
Energy
HX
H X ** H+--X-
HX+ H+ X+
e-
HX+ H+ X+
e-
e-
+
HX REMPI:
IE limit
v´
J´
v´
J´
Re
lati
ve
in
ten
sit
y
/a.u
.
80.05x103
80.0079.9579.9079.85Wavenumber 2h /cm
-1
Q0123456
V1(m+8)
79Br
+
Br atomicline7
270 cm-1
350x103
300
250
200
150
100
50
Re
lati
ve
in
ten
sit
y
/a.u
.
81.45x10381.4081.3581.3081.2581.2081.15
Wavenumber 2h/cm-1
I1 Q
2468
P234567
R2 3 4 5 6 7 8
S2 3 4 5 6
79Br+
H79Br+
V 1+(v´=m+10)
500x103
400
300
200
100
0
Rel
ati
ve
inte
ns
ity
/a
.u.
80.00x10379.9579.9079.85
Wavenumber 2h /cm-1
Q0123456
V1(m+8)
H79
Br+
79Br
+
Atomic line
7
180x103
160
140
120
100
80
E [
cm-1
]
4321r [Å]
H + Cl*(2P)
H* + Cl
H + Cl+
H+ + Cl
X(HCl+)
2
HCl** 1
F(HCl*)
1 V(H+Cl
-)
1
180x103
160
140
120
100
80
E [
cm-1
]
4321r [Å]
H + Cl*(2P)
H* + Cl
H + Cl+
H+ + Cl
X(HCl+)
2
HCl** 1
F(HCl*)
1 V(H+Cl
-)
1
85.3685.3585.3485.33x10
3
H35Cl+
35Cl+
Q
J´=J´´ = 9 8 7 6 5 4 3 2
HCl, F12
2h/ cm-1
Inte
nsi
ty
4x106
3
2
1
0
-1
-2
Rel
ativ
e In
ten
sity
86.4x10386.286.085.885.6
Wavenumber 2hv/cm-1
85.9285.9085.8885.86
x103
35Cl+
H35Cl+
Q
QQ 05
0
0
2468
V1
E1 V1
r(H-X)
Energy
HX
H X ** H+--X-
HX+/HX+ H+ X+
e-
e-
+
HX REMPI:
IE limit
v´
J´
v´
J´
State
Interactions ?
(1) / 0 (2) / 01 2
c101
a
c202= +
b =c1
´0 c2´0-
1 2
c1c2+2 2
= 1
E
WEci
2
4
2
12
12
2
2
E
W 12:
Interaction
strength
(1) / 0 (2) / 01 2
c101
a
c202= +
b =c1
´0 c2´0-
1 2
c1c2+2 2
= 1
E
WEci
2
4
2
12
12
2
2
E
(1) / 0 (2) / 01 2
c101
a
c202= +
b =c1
´0 c2´0-
1 2
c1c2+2 2
= 1
E
WEci
2
4
2
12
12
2
2
E( ) E(J´)E
E
85.3685.3585.3485.33x10
3
H35Cl+
35Cl+
Q
J´=J´´ = 9 8 7 6 5 4 3 2
HCl, F12
2h/ cm-1
Inte
nsi
ty
87.6x103
87.4
87.2
87.0
86.8
E v
´,J´
/ cm
-1
-120 -100 -80 -60 -40 -20 0 EJ´+1,J´ / cm
-1
V state
v´=13
v´=14
v´=1
F state
J´=8 J´=8
x
EJ´=8 =11.3 cm-1
HCl:
F12
V1
c12 c2
2
122 ,WEci
X ?
85.3685.3585.3485.33x10
3
H35Cl+
35Cl+
Q
J´=J´´ = 9 8 7 6 5 4 3 2
HCl, F12
2h/ cm-1
Com-press-ion
E x p a n s i o n
Inte
nsi
ty
87.6x103
87.4
87.2
87.0
86.8
E v
´,J´
/ cm
-1
150100500-50-100 dEJ´+1,J´ / cm
-1
V state
v´=14
v´=1
F state
J´=8
J´=7
J´=8
J´=7
F (v´=1)
fig.3c
87.6x103
87.4
87.2
87.0
86.8
E v
´,J´
/ cm
-1
150100500-50-100 dEJ´+1,J´ / cm
-1
V state
v´=14
v´=1
F state
J´=8
J´=7
J´=8
J´=7
F (v´=1)
fig.3c
2/120
201
2
1202
01 )(4
2
1
2
1EEWEEEi
87.6x103
87.4
87.2
87.0
86.8
E v
´,J´
/ cm
-1
-120 -100 -80 -60 -40 -20 0 EJ´+1,J´ / cm
-1
V state
v´=13
v´=14
v´=1
F state
J´=8 J´=8
x
EJ´=8 =11.3 cm-1
HCl:
F12
V1
c12 c2 = 0.42
122 ,WEci
X ?6 cm-1
from line shifts
r(H-X)
Energy
HX
H X ** H+--X-
HX+/HX+ H+ X+e-
e-
+
HX REMPI:
IE limit
v´
J´
v´
J´c1
2 c22
? X+
r(H-X)
Energy
HX
H X ** H+--X-
HX+/HX+ H+ X+e-
e-
+
HX REMPI:
v´
J´
v´
J´
H + X
X+
r(H-X)
Energy
HX
H X ** H+--X-
HX+/HX+ H+ X+e-
e-
+
HX REMPI:
v´
J´
v´
J´
HX*** H + X*
X+
r(H-X)
E
HX
H+--X-
HX+/HX+ H+ X+e- HX REMPI:
v´
J´
v´
J´c1
2 c22
X+
X
X*
c1 c2+2 2
I (HX+) =
c1 c2+2 2
I (X+) =
Ry: I.P./V:
)1(
)1(
)(
)(22
22
c
c
HXI
XI
c22
c22
= X+)/X+)= X+) /X+)= X+)/X+)
r(H-X)
E
HX
H+--X-
HX+/HX+ H+ X+e- HX REMPI:
v´
J´
v´
J´c1
2 c22
X+
X
X*
)1(
)1(
)(
)(22
22
c
c
HXI
XI
c22
c22
= X+)/X+)
= X+)/X+)
Exp.Q
i=35 i=37
I(i C
l+)/
I(H
i Cl+
)
Exp.Q
Calc. V,v´ = 20
Calc. V,v´=20
j3-1; ´=0
isotopomers H35Cl H37ClJ´ closest resonances(J´res) 2 2|E(J´res) | / cm-1 20.6 14.7W12(J´res) / cm-1 6.5 5.8c1
2 (c22) (J´res) 0.89(0.11) 0.81(0.19)
3.5 4.2 14 x 10-3 13 x 10-3
HiCl j 3-1
>
><
K. Matthíasson et al.J. Chem. Physics,134, 164302, (2011)
r(H-X)
Energy
HX
HX**
H+--X-
HX+/HX+ H+ X+e- HX REMPI:
v´
J´
v´
J´
H + X
X+
j 3-1
t 3+1 S/O
-0.005
0.005
0.015
0.025
0.035
0.045
0.055
2 3 4 5 6 7
J'
-0.005
0.005
0.015
0.025
0.035
0.045
0.055
2 3 4 5 6 7 8
J'
H35Cl f 32 f 31
I(35
Cl+
)/I(
H35
Cl+
)
States f32 f31
J´ closest resonances(J´res) 5 6|E(J´res) | / cm-1 17.7 27.9W12
max(J´res)/ cm-1 2 4c1
2(J´res) 0.987 0.979 4.0 0.5 0 1.0 x 10-3
<
>
Exp.Q
Calc.V,v´=9
Exp.S
Calc.V,v´=8
<
-0.005
0.005
0.015
0.025
0.035
0.045
0.055
2 3 4 5 6 7
J'
-0.005
0.005
0.015
0.025
0.035
0.045
0.055
2 3 4 5 6 7 8
J'
H35Cl f 32 f 31
I(35
Cl+
)/I(
H35
Cl+
)
Exp.Q
Calc.V,v´=9
Exp.S
Calc.V,v´=8
No dissociation
No predissociation pathway
Dissociation:
Predissociation by S/Ocouplings via “Gateway Rydberg states (1,3)”:
H37Cl j 3- (0+)
Exp. Q
89.8
89.6
89.4
89.2
x103
J´=0
J´=6
J´=6 v´=21
J´=6 v´=20
J´=0
J´=0
:
:
j 3- (0+), v´=0
V 1(0+)
H37Cl
Near resonance
S´=0 ´=0
E/c
m-1
Calc. V,v´=20 V,v´=21
H37Cl j 3- (0+)
Exp. Q
V´ states v´=20 v´=21J´ closest resonances(J´res) 6|E(J´res) | / cm-1 65W12
(J´res) / cm-1 25 25c1
2(J´res) 0.82 4.0(52 x 10-3) 4.0(52 x 10-3)
Rel
ativ
e In
ten
sity
77.98x103
77.9677.9477.9277.9077.8877.86
Wavenumber 2hv/cm-1
Q
02489 7 6
E1
79Br
H79
Br
10
H79Br
79.8
79.6
79.4
79.2
x103
J´=0
J´=6
J´=9J´=6 v´=m+5
H79Br
E 1(0+), v´=0
J´=9 v´=m+4
J´=0
V 1(0+)
Off resonance
S S´=0 ´=0
J´=6
J´=0
E/c
m-1
H79Br, E(v´=0)
I(79Br+)/I(H79Br+) Linewidth/cm-1
::Victor Huasheng Wang
Kristján MatthíassonJingming Long
Helgi Rafn Hróðmarsson
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