The SOLEIL view on sulfur rich oxides: The S2O bending mode ν2ν2 at 380 cm−1 and its analysis using an Automated Spectral Assignment Procedure (ASAP)

Abstract The fundamental vibrational bending mode ν 2 of disulfur monoxide, S2O, and the associated hot band 2 ν 2 - ν 2 have been observed at high spectral resolution for the first time at the SOLEIL synchrotron facility using Fourier-transform far-infrared spectroscopy. This transient species has been produced in a radio-frequency discharge by flowing SO2 over elemental sulfur. The spectroscopic analysis has been performed using the newly developed Automated Spectral Assignment Procedure (ASAP) which has enabled the accurate determination of more than 3500 energy levels of the v 2 = 1 and 2 vibrational states. The procedure provides a fast and convenient way to analyze large data sets in a straightforward manner, if one of the two vibrational states involved in the transition is accurately known from prior work. In addition to the high-resolution synchrotron study, pure rotational spectra of S2O in the v 2 = 1 and 2 vibrational states were observed in the frequency range 250–500 GHz by absorption spectroscopy in a long-path absorption cell. From these combined measurements, extensive molecular parameter sets have been determined, including full sets of sextic and two octic centrifugal distortion terms. Highly accurate band centers (to better than 10 - 5  cm−1) have been derived for both vibrational bands.

[1]  Chris W. Brown,et al.  Infrared spectra of matrix isolated disulfur monoxide isotopes , 1975 .

[2]  Oleg Chubar,et al.  The AILES Infrared Beamline on the third generation Synchrotron Radiation Facility SOLEIL , 2006 .

[3]  P. Roy,et al.  The far infrared spectrum of naphthalene characterized by high resolution synchrotron FTIR spectroscopy and anharmonic DFT calculations. , 2013, Physical chemistry chemical physics : PCCP.

[4]  L. Andrews,et al.  Infrared spectra and structures of isotopically enriched sulfur (S3 and S4) in solid argon , 1991 .

[5]  V. Horneman,et al.  Transferring calibration from CO2 laser lines to far infrared water lines with the aid of the ν2 band of OCS and the ν2, ν1 − ν2, and ν1 + ν2 bands of 13CS2: Molecular constants of 13CS2 , 2005 .

[6]  R. J. Myers,et al.  The microwave spectrum, structure, and dipole moment of disulfur monoxide , 1959 .

[7]  Durell S. Desmond,et al.  Analysis of high resolution FTIR spectra from synchrotron sources using evolutionary algorithms , 2015 .

[8]  F. Matsushima,et al.  Frequency measurement of pure rotational transitions in the v2 = 1 state of H2O , 2006 .

[9]  F. Lovas,et al.  Spectroscopic studies of the SO2 discharge system. I. The microwave spectrum and structure of S2O , 1974 .

[10]  Kojiro Takagi,et al.  Frequency measurement of pure rotational transitions of H20 from 0.5 to 5 THz , 1995 .

[11]  W. Meerts,et al.  Analysis of the FTIR spectrum of pyrazine using evolutionary algorithms , 2009 .

[12]  H. Jones,et al.  The diode-laser spectrum of the ν1 band of disulfur monoxide , 1985 .

[13]  Štěpán Urban,et al.  Advanced graphical software for assignments of transitions in rovibrational spectra , 2007 .

[14]  H. Rudolph,et al.  The equilibrium structure of disulfur monoxide: Diode laser spectroscopy of ν1 and ν3 of S218O and ν3 of S216O , 1986 .

[15]  R. J. Myers,et al.  Disulfur Monoxide. III. Its Infrared Spectrum and Thermodynamic Functions , 1965 .

[16]  G. Winnewisser,et al.  The centrifugal distortion constants of disulfur monoxide , 1973 .

[17]  E. Herbst,et al.  Rotational spectrum of trans–trans diethyl ether in the ground and three excited vibrational states , 2005 .

[18]  Pablo A. Denis,et al.  Theoretical characterisation of the SSO, cyclic SOS and SOS isomers , 2010 .

[19]  O. Pirali,et al.  High resolution far-infrared Fourier transform spectroscopy of radicals at the AILES beamline of SOLEIL synchrotron facility. , 2011, The Review of scientific instruments.

[20]  R. Steudel.  Sulfur-Rich Oxides S n O and S n O 2 ( n >1) , 2003 .

[21]  S. Schlemmer,et al.  Millimeter- and submillimeter-wave spectroscopy of disulfur dioxide, OSSO , 2015 .

[22]  D. Clouthier,et al.  Supersonic jet spectroscopy of S2O , 1988 .

[23]  H. Müller,et al.  Rotational spectroscopy of S2O: Vibrational satellites, 33S isotopomers, and the sub-millimeter-wave spectrum , 2006 .

[24]  Herbert M. Pickett,et al.  The fitting and prediction of vibration-rotation spectra with spin interactions , 1991 .

[25]  O. Pirali,et al.  The far-infrared spectrum of azulene and isoquinoline and supporting anharmonic density functional theory calculations to high resolution spectroscopy of polycyclic aromatic hydrocarbons and derivatives. , 2014, The Journal of chemical physics.

[26]  J. Lindenmayer.  The rs structure of disulfur monoxide: the microwave spectrum of S218O , 1986 .

[27]  J. Stanton,et al.  Rotational spectroscopy and equilibrium structures of S3 and S4. , 2005, The Journal of chemical physics.