Tetrasulfur, S4: Rotational spectrum, interchange tunneling, and geometrical structure

Details Tetrasulfur, S4: Rotational spectrum, interchange tunneling, and geometrical structure Tetrasulfur, S4: Rotational spectrum, interchange tunneling, and geometrical structure

Jul 2004

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2004jchph.121..632m&link_type=abstract

Journal of Chemical Physics, Volume 121, Issue 2, pp. 632-635 (2004).

Physics

Chemical Physics

8

Rotational Analysis, Radio-Frequency And Microwave Spectra, Line And Band Widths, Shapes, And Shifts, Vibrational Analysis, Rotation, Vibration, And Vibration-Rotation Constants, Interatomic Distances And Angles, General Molecular Conformation And Symmetry, Stereochemistry

Scientific paper

The rotational spectrum of S4 has been observed for the first time in an electrical discharge through sulfur vapor. Two techniques have been used: Fourier transform microwave spectroscopy and long-path millimeter-wave absorption spectroscopy. Small, but systematic shifts of the measured transition frequencies of the normal isotopic species indicate that S4 has C2v symmetry but with a low-lying transition state of D2h symmetry, yielding interchange tunneling at 14.1(2) kHz in its ground vibrational state. From the rotational constants of the normal and the single 34S isotopic species, an experimental (r0) structure has been derived: S4 is a singlet planar trapezoid with a terminal bond length of 1.899(7) Å, a central bond of 2.173(32) Å, and an S-S-S angle of 103.9(8)°. Like thiozone (S3), S4 is a candidate for detection in the atmosphere of the Jovian moon Io and in other astronomical sources.

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