1
N. NISHIMIYA and T. YUKIYA
Tokyo Polytechnic University, Kanagawa, JAPAN.
HIGH – RESOLUTION LASER SPECTROSCOPY OF THE A3Π1 ← X 1Σ+ SYSTEM OF ICl
IN 0.8 m REGION
2
Our Research
Laser spectroscopy of electronic band system of halide molecules. Target: ICl, IBr, I2, and Br2 For establishing the frequency standard in the near infrared region. In this time we have measured the A-X spectra of ICl in the region of
11300-14450 cm-1 region. ICl spectrum is weak comparing to other halogen molecules. It is easy to assign, because of its wide spectrum intervals. One spectrum at least can be found within a continuous tuning range of a
titanium sapphire laser in the 0.8 m region. The constants have determined by taking into consideration isotopic r
educed mass ratio.
3
References(1) J.A.Coxon,et. al. ,``The A31u X1+ Absorption Spectrum of ICl. '', J.Mol.Spectrosc.79,
363 (1980)
(2) J.A.Coxon and M.A.Wickramaaratchi,``The A31 X1+ Emission Spectrum of ICl in the Near Infrared. '', J.Mol.Spectrosc.79, 380 (1980)
(3) J.C.DBrand and A.R.Hoy,``High Vibrational Level of the the X state of ICl, and the Electronic-Coriolis Coupling of the X and A states.'',J.Mol.Spectroscopy, 114, 197 (1985)
(4) J.C.D.Brand, et.al. ``The A’(32) of ICl”, J.Mol.Spectrosc., 113, 388 (1985)
(5) H.G.Hedderich, et.al.,``The High-Resolution Infrared Spectrum of Iodine Monochloride.'', J.Mol.Spectrosc., 155, 384 (1992).
(6) C.M.Western, ``Variation of the electronic wave function with internuclear separation: High-resolution spectroscopy of the A3 state of I35Cl near the dissociation limit.’’, J.Chem.Phys., 98, 1826 (1993)
(7) T.J.Slotterback, et.al.,``Hyperfine measurements in the X and B electronic states of I35,37Cl: Probing the ionic character of the chemical bond.'', J.Chem.Phys., 101, 7221(1994)
(8) T.J.Slotterback, et.al.,``Hyperfine analysis of the mixed A31 v=28 and X1+ v=69 states of I35Cl”, J.Chem.Phys., 103, 9125(1994)
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J+1(odd)
+
f-levele-level
J=0Q
Type doubling
J=-1P
J=1RJ(even)
Energy
Internuclear distance r
J+1(odd)
J(even)
-
e-levelf-level
-+
+-
Potential Energy
P and R line shape
5
15Hz
400 MHzFrequency Modulation:Saturated Vapor at Room Temp.Cell Temperature and Gas Pressure:
14.4mOptical Path Length:
Conditions
Lock in Amp.
Lock in Amp.
Wave MeterOpt. Fiber
GeneratorFunction
PC
BusLocal
M
M
BS
BS
BS
Lock in Amp.
M
Ti:Al2O3Laser
ControllerLaser
Sweep signal
Etalon Driven Signal
BRF Driven Signal D/AServo Amp.
Ar+ Ion Laser
BS
Confocal Cavity
Power MonitorPD
PD
GP-IB Bus
PDAbsorption Cell (White Cell)
L
Osc.
Block Diagram of The Ti:Sapphire Ring Laser Spectrometer.
6
Recorder Trace of the Absorption Lines in 12600 cm-1 Region
7
Fortrat Diagram of I35Cl
1 2 3 4 50 6 7
12345
0
67II3535ClCl
v’v’
v”v”P,Q,R-Blanches
Only Q-Blanches
v”v”
0
3 5 7 7
4
3
4
4
10 0 0
cm-1
8
II3535ClCl v’=0-7T’0 ,T’1 , ,T’7B’0e ,B’1e , ,B’7e
B’0f ,B’1f , ,B’7f
D’0 ,D’1 , ,D’7H’0 ,H’1 , ,H’7
II3535ClCl v’=0-7T’0 ,T’1 , ,T’7B’0e ,B’1e , ,B’7e
B’0f ,B’1f , ,B’7f
D’0 ,D’1 , ,D’7H’0 ,H’1 , ,H’7
II3737ClCl v’=0-6T’0 ,T’1 , ,T’6B’0e ,B’1e , ,B’6e
B’0f ,B’1f , ,B’6f
D’0 ,D’1 , ,D’6H’0 ,H’1 , ,H’6
II3737ClCl v’=0-6T’0 ,T’1 , ,T’6B’0e ,B’1e , ,B’6e
B’0f ,B’1f , ,B’6f
D’0 ,D’1 , ,D’6H’0 ,H’1 , ,H’6II3535Cl / ICl / I3737ClCl
Y10’’ , Y20’’ , Y30’’Y01’’, Y11’’ , Y21’’
Y02’’, Y12’’ Y03’’, Y13’’
II3535Cl / ICl / I3737ClClY10’’ , Y20’’ , Y30’’Y01’’, Y11’’ , Y21’’
Y02’’, Y12’’ Y03’’, Y13’’
0 0)2/(
,,
32222/
)1(2
1
)1()1()1(
l
m
m
l
lmml
ml
vvfvevvJ
JJvY
Y
JJHJJDJJBTE
The Coefficients of the Power Expansion for the A and the X State
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The Spectroscopic Constants of The X State
In cm-1 and 2.5 in parentheses=0.0022 cm-1
Y’’10 384.29416 Y’’01 0.114157656
=0.0021 cm-1
1)
Type B( constrain Y’’10 and Y’’01)
Type A(All parameter is variable.)
H.G.Heddrich and P.F.Bernath ,J.Mol.Spectrosc.155.384-392(1992)
=0.0022 cm-1
2) Y’’03 is calculated using 152
1,0
0,11,14
0,1
51,0
3,0 107243.816
316
Y
YY
Y
YY
Type C( constrain Y’’10, Y’’01 and Y’’03)
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The Spectroscopic Constants of The A State
II3535ClCl
II3737ClCl
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Relationship between Tv and Vibrational Level
13800
14000
14200
14400
14600
14800
15000
15200
0 1 2 3 4 5 6 7
T’v
v
II3737ClClII3535ClCl
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Deviation of Tv from the (v+1/2) Polynomial
-0.165
-0.160
-0.155
-0.150
-0.145
-0.140
-0.135
-0.130
-0.125
-0.120
0 1 2 3 4
II3535ClCl
II3737ClClTv
v
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Relationship between Bvf and Qv and Vibrational Level
0.076
0.078
0.080
0.082
0.084
0 1 2 3 4 5 6 7
B’vf
v
II3535ClCl
II3737ClCl0.80
0.90
1.00
1.10
1.20
1.30
0 1 2 3 4 5 6
Qv x 105
II3737ClCl
II3535ClCl
v
14
Relationship between Dv and Hv and Vibrational Level
4.55.05.56.06.57.07.58.0
0 1 2 3 4 5 6 7
D’v x108
II3535ClCl
II3737ClCl
v-4.0-3.5-3.0-2.5-2.0-1.5-1.0-0.50.0
0 1 2 3 4 5 6 7
H’v x1013
II3535ClCl
II3737ClCl
v
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Average Line Splittings of Vibrational Level in the P- and R-Branches
0.000
0.005
0.010
0.015
0.020
0.025
0.030
0.035
0.040
0 1 2 3 4 5 6
0.0317cm-1
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Summary
A – X system of P,Q,R-branch lines were assigned. 4900 lines
X-state of Dunham coefficients were determined by using a mass-reduced least square fitting procedure. 7 parameters
Spectroscopic constants of A-state were calculated . Tv, Bvf, qv, Dv, Hv for each vibrational levels (Dunham coefficients are not suitable for A- state.)