1. The Rotational Spectrum of cis- and trans-HSSOH
M. Koerber, O. Baum, T. Giesen, S. Schlemmer
(RH03)
I. Physikalisches Institut, Universität zu Köln, Germany
63rd International Symposium on Molecular Spectroscopy

2. Motivation H2S2 HSOH H2O2 Monika Koerber
Behrend et al.,
J. Mol. Spec. (1991)
Baum et al.,
J. Mol. Struc. (2006)
Flaud et al.,
J. Chem. Phys. (1989)
Monika Koerber
The Rotational Spectrum of cis- and trans-HSSOH
RH03

3. WANTED Motivation trans-H2O3 H2O3 trans-H2S3 H2S3 cis-H2S3 trans-HSSOH
K. Suma et al.,
J. Am. Chem. Soc., 127,
(2005)
M. Liedke et al.,
J. Mol. Struc. 413, (1997)
WANTED
trans-HSSOH
cis-HSSOH
Monika Koerber
The Rotational Spectrum of cis- and trans-HSSOH
RH03

4. All Solid-State Spectrometer
Experimental Setup
All Solid-State Spectrometer
Range:
GHz
Output power:
2 - 6 mW
Monika Koerber
The Rotational Spectrum of cis- and trans-HSSOH
RH03

5. Flash vacuum pyrolysis of t-BuS(O)St-Bu
Synthesis of HSSOH
Flash vacuum pyrolysis of t-BuS(O)St-Bu
~ 500°C
~ 700°C
tert-butylthiosulfinic acid
S-tert-butylester
C8H18S2O
tert-butylthiosulfoxylic acid
+ 2-methylpropene
C4H10S2O + C4H6
1-oxatrisulfane
+ 2x 2-methylpropene
HSSOH + 2x C4H6
Königshofen et al., Z. Anorg. Allg. Chem. 625, (1999):
Study of absorption bands in the IR for different pyrolysis temperatures,
no rotational resolved spectra
Monika Koerber
The Rotational Spectrum of cis- and trans-HSSOH
RH03

6. Characterization of byproducts
Nicht nur mono-molekularer Zerfall in der Gasphase – SO2
pyrolysis
at 700°C
Monika Koerber
The Rotational Spectrum of cis- and trans-HSSOH
RH03

7. Characterization of byproducts
Monika Koerber
The Rotational Spectrum of cis- and trans-HSSOH
RH03

8. Spectral features trans-HSSOH µb = 0.99(3) µc cis-HSSOH µb = 0.29(3)
calc. µa µb µc
µb/µc
trans-
HSSOH
0.980
cis-
HSSOH
0.5380
-0.247
J.Gauss, priv. comm. (2006)
cis-HSSOH
cis-HSSOH µb
= 0.29(3) µc
Monika Koerber
The Rotational Spectrum of cis- and trans-HSSOH
RH03

9. Relying on calculated line intensities, it follows
Spectral features
Relying on calculated line intensities, it follows
from the relative intensities of the measured lines:
[trans-HSSOH]
trans conformer is at least
two times more abundant
= 2.2(3)
[cis-HSSOH]
Monika Koerber
The Rotational Spectrum of cis- and trans-HSSOH
RH03

10. Fortrat diagram trans-HSSOH cis-HSSOH Monika Koerber
Watson-type Hamiltonian
in S-Reduction
Monika Koerber
The Rotational Spectrum of cis- and trans-HSSOH
RH03

11. Rotational Parameters
trans-HSSOH
cis-HSSOH
calc. (Gauss)*
exp. (this work)
A0 (MHz)
(104)
(70)
B0 (MHz)
4481.7
(65)
(35)
C0 (MHz)
3826.3
(65)
(35)
near prolate symmetric rotors
225 lines
201 lines
J‘‘max = 77
J‘‘max = 80
Ka‘‘max = 9
Ka‘‘max = 9
* CCSD(T)/cc-pCVQZ + MP2/cc-pVTZ (vibr. corr.)
Monika Koerber
The Rotational Spectrum of cis- and trans-HSSOH
RH03

12. Rotational Parameters
trans-HSSOH
cis-HSSOH
calc. (Gauss)*
exp. (this work)
A0 (MHz)
(104)
(70)
B0 (MHz)
4481.7
(65)
(35)
C0 (MHz)
3826.3
(65)
(35)
DJ (kHz)
2.1875
(251)
(188)
DK (kHz)
(64)
(28)
DJK (kHz)
(173)
(119)
d1 (kHz)
(35)
(33)
d2 (kHz)
(247)
(254)
HJ (mHz) -
-67.34(83)
HKJ (mHz)
-522.2(258)
-630.1(286)
h1 (mHz)
0.7198(202)
0.7469(215)
h2 (mHz)
0.4458(183)
0.3372(223)
rms
0.53
0.68
* CCSD(T)/cc-pCVQZ + MP2/cc-pVTZ (vibr. corr.)
Monika Koerber
The Rotational Spectrum of cis- and trans-HSSOH
RH03

13. Classification of pyrolysis products according to the
Conclusion
Classification of pyrolysis products according to the
temperature behaviour of their rotational lines
First detection of the two most stable conformers of HSSOH
Determination of rotational constants and distortion
coefficients up to sextic level and µb/µc ratio
Estimation of [trans-HSSOH]/[cis-HSSOH] ratio
Excellent agreement of experimental data with
high-level ab initio values
Monika Koerber
The Rotational Spectrum of cis- and trans-HSSOH
RH03

14. Measure a-type rotational transitions (parallel spectra)
Outlook
Measure a-type rotational transitions (parallel spectra)
Determination of experimental structure for HSSOH
Measure Isotopologues
Find new synthesis pathway for D-Isotopologues
RF discharge as done for HSOH possible?
Monika Koerber
The Rotational Spectrum of cis- and trans-HSSOH
RH03