e quilibrium s tructure of the s imple s kew c hain m olecule hsoh 61 th international symposium on...
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EQUILIBRIUM STRUCTURE OF THE SIMPLE SKEW CHAIN MOLECULE HSOH
61th International Symposium on Molecular Spectroscopy, Ohio June, 22. 2006
Oliver Bauma, Jürgen Gaussb, Stephan Schlemmera, Thomas Giesena
a I. Physikalisches Institut, Universität zu Köln, Germanyb Institut für Physikalische Chemie, Universität Mainz, Germany
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Outline
Oliver Baum (RE03)
Equilibrium Structure of the Simple Skew Chain Molecule HSOH
International Symposium on Molecular Spectroscopy, Ohio
Previous works
Results
Synthesis
Experimental details
Motivation
Conclusion
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Equilibrium Structure of the Simple Skew Chain Molecule HSOH Motivation
Oliver Baum (RE03)International Symposium on Molecular Spectroscopy, Ohio
H2SOn
(n=1-4)
Structure
internal rotation„missing“ link
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Equilibrium Structure of the Simple Skew Chain Molecule HSOH Previous works
Oliver Baum (RE03)International Symposium on Molecular Spectroscopy, Ohio
Structure
since 1973 More than 20 theoretical papers deal with structure and/or barrier
1973-2002 Only 2 experimental publications
Matrix reactions of oxygen atoms with H2S moleculesR. R. Smardzewski and M.C. Lin; J. Chem. Phys. 66 (1977), 3197
Experimental evidence for the gas phase existence of HSOH (hydrogen thioperoxide) and SOH2 (thiooxonium ylide)
M. Iraqi and H. Schwarz; Chem. Phys. Lett. 221 (1994), 359-362
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Equilibrium Structure of the Simple Skew Chain Molecule HSOH Previous works
Oliver Baum (RE03)International Symposium on Molecular Spectroscopy, Ohio
Structure
since 1973
1973-2002
since 2003 5 experimental publicationsGas-Phase Detection of HSOH: Synthesis by Flash Vacuum Pyrolysis of Di-tert-butyl Sulfoxide
and Rotational-Torsional SpectrumG. Winnewisser et al.; Chem. Eur. J. 9 (2003), 5501-5510
Gas-Phase detection of discharge-generated DSODM. Behnke et al.; J. Mol. Spec. 221(1) (2003), 121-126
Asymmetric rotor analysis of DSOD spectra up to the rQ3 branch near 653GHz
S. Brünken et al.; J. Mol. Struct. 742 (2005), 237-242
Gas-phase detection of HSOD and empirical equilibrium structure of oxadisulfane
O. Baum et al.; J. Mol. Struct. (2006) (in press)
Low-Pressure Pyrolysis of tBu2SO: Synthesis and IR Spectroscopic Detection of HSOHBeckers et al.; Chem. Eur. J. 12 (2006), 832-844
H34SOH
More than 20 theoretical papers deal with structure and/or barrier
Only 2 experimental publications
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Oliver Baum (RE03)
Equilibrium Structure of the Simple Skew Chain Molecule HSOH
International Symposium on Molecular Spectroscopy, Ohio
Di-tert-butylsulfoxide
ca. 500°C
tert-Butylsulfenic acid
ca. 1200°C
Oxadisulfane
HSOH
H34SOH
D2O+D2S DSODRF-discharge
HDO+S8 HSODRF-discharge
Synthesis
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Synthesis
Oliver Baum (RE03)
Equilibrium Structure of the Simple Skew Chain Molecule HSOH
International Symposium on Molecular Spectroscopy, Ohio
Synthesis
Di-tert-butylsulfoxide
ca. 500°C
tert-Butylsulfenic acid
ca. 1200°C
Oxadisulfane
HSOH
H34SOH
D2O+D2S DSODRF-discharge
HDO+S8 HSODRF-discharge
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Oliver Baum (RE03)
Equilibrium Structure of the Simple Skew Chain Molecule HSOH
International Symposium on Molecular Spectroscopy, Ohio
Synthesis
Di-tert-butylsulfoxide
ca. 500°C
tert-Butylsulfenic acid
ca. 1200°C
Oxadisulfane
HSOH
H34SOH
D2O+D2S DSODRF-discharge
HDO+S8 HSODRF-discharge
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Cologne Terahertz Spectrometer
Oliver Baum (RE03)
Equilibrium Structure of the Simple Skew Chain Molecule HSOH
International Symposium on Molecular Spectroscopy, Ohio
BWOs (ISTOK Corp., Russia) high power radiation sources (150-950 GHz with different tubes)
down-conversion of the BWO-signal on a harmonic mixer and phase locking of the mixed signal (350 MHz) to a rubidium reference
variable frequency modulation of the source and demodulation of the signal by a lock-in amplifier
liquid Helium cooled InSb hot electron bolometer (QMC Inc, UK) as detector
Experimental details
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HDO+S8(H2O:HDO:D2O = 1:2:1)
HDO+S8
Experimental details
Oliver Baum (RE03)
Equilibrium Structure of the Simple Skew Chain Molecule HSOH
International Symposium on Molecular Spectroscopy, Ohio
typical spectrum
byproducts ?
HSOH ?
HSOD ?DSOD ?SO2 ?
S2O ?
S3 ?
discrimination of byproducts
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H2O+S8
HDO+S8(H2O:HDO:D2O = 1:2:1)
D2O+S8
HDO+S8
Experimental details
Oliver Baum (RE03)
Equilibrium Structure of the Simple Skew Chain Molecule HSOH
International Symposium on Molecular Spectroscopy, Ohio
discrimination of byproducts
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HDO+S8(H2O:HDO:D2O = 1:2:1)
HDO+S8
H2O+S8
D2O+S8
Torsional splitting in HSOH (rQ1): 112,10 111,10
Experimental details
Oliver Baum (RE03)
Equilibrium Structure of the Simple Skew Chain Molecule HSOH
International Symposium on Molecular Spectroscopy, Ohio
discrimination of byproducts
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c-type transitions b-type transitions
HSOD rQ2-branch
experimental values
Experimental details
Oliver Baum (RE03)
Equilibrium Structure of the Simple Skew Chain Molecule HSOH
International Symposium on Molecular Spectroscopy, Ohio
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experimental
calculated
J3,J-2 J2,J-2
HSOD rQ2-branch
J=88
8
9
9
J=910
10
J=1011
11
J=1112
12
J=12131415
29 30 31
7
J3,J-3 J2,J-1
JKa,Kc
Experimental details
Oliver Baum (RE03)
Equilibrium Structure of the Simple Skew Chain Molecule HSOH
International Symposium on Molecular Spectroscopy, Ohio
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experimental structure
HSOH experimental
A0 (MHz) 202069.05431(134)
B0 (MHz) 15281.956620(123)
C0 (MHz) 14840.216440(121)
G. Winnewisser et al. (2003)
DSOD experimental
A0 (MHz) 106850.4937(55)
B0 (MHz) 13865.38319(173)
C0 (MHz) 13173.54491(227)
S. Brünken et al. (2005)
HSOD experimental
A0 (MHz) 159969.277(303)
B0 (MHz) 14132.113(37)
C0 (MHz) 14020.600(38)
O. Baum et al. (2006)
H34SOH experimental
A0 (MHz) 201739.7641(129)
B0 (MHz) 15001.43940(38)
C0 (MHz) 14573.77816(39)
G. Winnewisser et al. (2003)
Results
Oliver Baum (RE03)
Equilibrium Structure of the Simple Skew Chain Molecule HSOH
International Symposium on Molecular Spectroscopy, Ohio
r
Bre BB
2
10
bI
hB
28v
experimental structure
re
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HSOH experimental
A0 (MHz) 202069.05431(134) 1431.9
B0 (MHz) 15281.956620(123) 118.7
C0 (MHz) 14840.216440(121) 136.3
G. Winnewisser et al. (2003)
DSOD experimental
A0 (MHz) 106850.4937(55) 513.9
B0 (MHz) 13865.38319(173) 89.1
C0 (MHz) 13173.54491(227) 106.8
S. Brünken et al. (2005)
HSOD experimental
A0 (MHz) 159969.277(303) 946.2
B0 (MHz) 14132.113(37) 107.5
C0 (MHz) 14020.600(38) 111.6
O. Baum et al. (2006)
H34SOH experimental
A0 (MHz) 201739.7641(129) 1431.1
B0 (MHz) 15001.43940(38) 116.0
C0 (MHz) 14573.77816(39) 133.1
G. Winnewisser et al. (2003)
Results
Oliver Baum (RE03)
Equilibrium Structure of the Simple Skew Chain Molecule HSOH
International Symposium on Molecular Spectroscopy, Ohio
„semi-experimental“ structure
re
r
Bre BB
2
10
r
r2
1
r
r2
1
r
r2
1
r
r2
1
experimental CCSD(T) / cc-pVTZ *
J. Gauss et al.*
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Oliver Baum (RE03)
Equilibrium Structure of the Simple Skew Chain Molecule HSOH
International Symposium on Molecular Spectroscopy, Ohio
Results
b
a b
cc
a
Geometrical parameter
Empirical re CCSD(T)/cc-pVQZ
R(SO) 1.6616(1) Å 1.6619 Å
R(SH) 1.3420(2) Å 1.3414 Å
R(OH)
(OSH)
(SOH)
(HSOH)
0.9606(3) Å
98.57(5)°
107.19(3)°
90.41(11)°
0.9601 Å
98.55°
107.1°
91.29°
*
J. Gauss et al.*
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Oliver Baum (RE03)
Equilibrium Structure of the Simple Skew Chain Molecule HSOH
International Symposium on Molecular Spectroscopy, Ohio
Results
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Oliver Baum (RE03)
Equilibrium Structure of the Simple Skew Chain Molecule HSOH
International Symposium on Molecular Spectroscopy, Ohio
Geometrical parameter
HSSH
J. Behrend et al. (1991)
HSOH
O. Baum et al. (2006)
HOOH
J.-M. Flaud et al. (1989)R(XX) 2.056 Å 1.6616(1) Å 1.456 Å
R(SH) 1.342 Å 1.3420(2) Å ---
R(OH)
(XSH)
(SOH)
(HSOH)
---
97.9°
---
90.3°
0.9606(3) Å
98.57(5)°
107.19(3)°
90.41(11)°
0.961 Å
---
102.3°
113.7°
Results
X = S,O
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Conclusion
aaa
We found a “simple way” to synthesize HSOH and its deuterated isotopomers
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We derived an empirical equilibrium structure of HSOH
HSOH is a molecule with many different traits
Vibrational dynamics of HSOH
Outlook
Oliver Baum (RE03)
Equilibrium Structure of the Simple Skew Chain Molecule HSOH
International Symposium on Molecular Spectroscopy, Ohio
The geometrical parameters from ab initio calculations are in very good agreement with the derived data
The structure of HSOH fits smoothly into those of its kin molecules HSSH and HOOH
HSSOH, HOSOH, … “simple way”
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