The Raman and infrared spectra of thiophosgene and its dimer have been reinvestigated and assignments based on new data and a normal coordinate analysis of the monomer are presented. The spectra obtained in gas, liquid, and solid phases are compared and two polymeric species and their spectra are discussed. A description of the fundamentals of thiophosgene is presented in terms of atom displacements, potential energy distributions, and Coriolis coupling coefficients. The transferability of the valence force field between thiophosgene and phosgene is demonstrated.

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The use of small spectral slitwidths complicates Raman intensity measurements of laser-excited spectra. The nature of the slit-function correction in medium-resolution laser-Raman instruments is discussed and some effects of asymmetric slit functions on asymmetric and symmetric Raman bands are explored. Corrections to bandwidth and band shape for nonideal slit functions are obtained from the concept of an intermediate standard which represents the pure slit function at some limiting spectral slitwidth. The corrections are applied to the contours of the Raman bands of CCl4 at 458 cm−1 and CH3OH at 1028 cm−1, and the corrected contour of the 1028-cm−1 band is compared to that obtained for the same band on a high-resolution laser-Raman spectrometer. A codification of Raman band shapes by means of two shape parameters is discussed.

Recent investigations of the Raman and infrared spectra of S2Br2 and S2Cl2 have reported new polarization data and the observation of previously unreported fundamentals. A normal coordinate analysis investigates the transferability of the valence force field for these molecules, and the results of these calculations are reported in terms of potential-energy distributions, vibrational mean amplitudes, Cartesian atom displacements, and Coriolis coupling coefficients. The respective spectra are discussed in light of these data, and a value for the S—S force constant is reported.