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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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.*

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.*

Oliver Baum (RE03)

Equilibrium Structure of the Simple Skew Chain Molecule HSOH

International Symposium on Molecular Spectroscopy, Ohio

Results

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

aaa

Conclusion

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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”