The vibrational spectrum and force constants of P₄S₃

Abstract

Abstract The Raman spectra of P 4 S 3 in the solid and molten states and in solution in CS 2 have been determined. It appeared impossible to obtain reliable quantitative depolarization factors; the assignment was therefore based on the visually estimated state of polarization. The spectra in CS 2 solution contained several unexplained frequencies, much higher than was to be expected. Force constants for the P‐S and P‐P bonds have been calculated, on the basis of the C 3v symmetry, assumed for the molecule. The values found are distinctly lower than those calculated with Badger's or Gordy's formulae from known bond distances. The calculations in the main support the structure for P 4 S 3 determined by electron diffraction and X‐ray analysis.