Symmetry Coordinates, Harmonic Force Field, and Mean Amplitudes for Light and Heavy Dibenzene Chromium

The rotational spectrum of the ClS2 free radical in the gaseous phase has been observed in the millimetre- and submillimetre-wave regions. The ClS2 radical was generated by a dc glow discharge in either S2Cl2 or SCl2. Both a- and b-type R-branch transitions, most of which were split into two fine structure components, were detected for both of the 35Cl and 37Cl isotopic species in the ground vibronic state. As expected from the small hyperfine interaction constants reported by an electron spin resonance (ESR) study, the hyperfine structure was resolved for none of the transitions observed in the present study. Analysis of the observed transition frequencies yielded rotational and centrifugal distortion constants and also spin–rotation interaction constants with their centrifugal corrections. The spin–rotation interaction constants obtained in the present study were consistent with g values of the ESR study. The rotational constants of the two isotopic species led to the structure parameters r(S—S) = 1.906 (7) Å, r(S—Cl) = 2.071 (5) Å, and θ(SSCl) = 110.3 (4)°. A harmonic force field was derived from the observed centrifugal distortion constants and inertial defects combined with the ν1 frequency reported in literature on electronic spectroscopy. This harmonic force field yielded the ν2 and ν3 frequencies (445 (21) and 213.0 (2) cm−1, respectively, for 35ClS2), which differed considerably from the values reported previously.

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Molecular Vibrations of Sulphur Trioxide. Accurate Determination of Harmonic Force Field, and Calculated Mean Amplitudes and Shrinkage Effect.

Acta Chemica Scandinavica ◽

10.3891/acta.chem.scand.21-1581 ◽

1967 ◽

Vol 21 ◽

pp. 1581-1586 ◽

Cited By ~ 5

Author(s):

R. Stølevik ◽

B. Andersen ◽

S. J. Cyvin ◽

J. Brunvoll ◽

G. Eriksson ◽

...

Keyword(s):

Force Field ◽

Accurate Determination ◽

Molecular Vibrations ◽

Harmonic Force ◽

Shrinkage Effect ◽

Sulphur Trioxide

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An ab initio study of many isomers of S2O2. A combined theoretical and experimental analysis of the harmonic force field and molecular structure of cis-planar OSSO

Chemical Physics ◽

10.1016/0301-0104(90)87068-m ◽

1990 ◽

Vol 141 (2-3) ◽

pp. 335-353 ◽

Cited By ~ 14

Author(s):

Colin J. Marsden ◽

Brian J. Smith

Keyword(s):

Molecular Structure ◽

Force Field ◽

Ab Initio ◽

Experimental Analysis ◽

Ab Initio Study ◽

Harmonic Force

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Symmetry Coordinates and Tentative Force Field Analysis of a PMo12O40 Model with the Keggin Structure

Zeitschrift für Naturforschung A ◽

10.1515/zna-1976-1221 ◽

1976 ◽

Vol 31 (12) ◽

pp. 1589-1600 ◽

Cited By ~ 2

Author(s):

Lennart Lyhamn ◽

S. J. Cyvin ◽

B. N. Cyvin ◽

J. Brunvoll

Keyword(s):

Experimental Data ◽

Force Field ◽

Force Constant ◽

Raman Spectra ◽

Vibrational Analysis ◽

Field Analysis ◽

Infrared And Raman Spectra ◽

Symmetry Coordinates ◽

Force Field Analysis ◽

Complex Ion

Abstract A complete vibrational analysis is performed for the 53 atomic PMo12O40 model of Td symmetry. The symmetry coordinates are classified into those of (a) ligand vibrations, (b) framework-ligand couplings, (c) framework vibrations, and (d) interligand vibrations. Simple valence force fields are estimated, and the influence of inclusion of redundancies on the calculated frequencies and symmetry force constants is investigated. Comments are made on calculated symmetry force constant values up to 345 mdyne/Å. Vibrational frequencies are calculated for the Mo3O7 and Mo3O13 units and for the PMo12O403- complex ion. For the latter compound the calculated values are compared with experimental data from infrared and Raman spectra.

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