Normal Coordinate Treatments and Calculated Thermodynamic Properties of Phosphoryl Fluorodichloride,Phosphoryl Chlorodifluoride,Thiophosphoryl Bromide,Thiophosphoryl Fluorodibromide,and Thiophosphoryl Bromodifluoride

The Raman and ir spectra of phosphoryl dichlorofluoride, phosphoryl difluorochloride, thiophosphoryl tribromide, thiophosphoryl dibromofluoride, and thiophosphoiyl difluorobromide were collected and examined for the most probable values for the wavenumbers, intensities, and depolarization factors. The data are as follows: The Raman displacements Δσ in cm⁻¹, the relative intensities I, and the depolarization factors ρ are for POFCl₂: Δσ (I) ρ = 207(3.6)0.55, 254(1.8)6/7, 330(1)0.6, 372(3.4)6/7, 386(5.5)0.3, 547(10)0.05, 620(w)6/7, 894(w)0.45, and 1331 (m)p; for POF₂Cl: 274(10)0.65, 274 (calculated), 410(17)0.23, 424(7)6/7, 424 (calculated), 618(10)0.05, 895(m)0.1, 948(w>)6/7, and 1358(m)0.2; for PSBr₃: 115(5.5)6/7, 165(4.1)0.3, 179(5)6/7, 299(10)0.05, 438(w)6/7, and 718 (m)p; for PSFBr₂:129(7)0.6, 159.5(11)6/7, 219(10)0.5, 254(4)6/7, 274(5)0.3, 377(10)0.2, 470(w)6/7, 718(m)p, and 887 (vw)p; and for PSF₂Br: 175(28)0.5, 231(3)6/7, 288(29)0.3, 298(w)6/7, 384(7)0.25, 462(w)0.1, 474(10)0.1, 711(9)0.1, 899(w)0.75, and 930(w)0.75. No published ir spectral data were found for POFCl₂, POF₂Cl, PSBr₃, PSFBr₂, and PSF₂Br. Also normal coordinate treatments were conducted for POFCl₂, POF₂Cl, PSFBr₂, and PSF₂Br on the basis of the C_s model and the one for PSBr₃ on the basis of the C_3v model. The results of these treatments established the above listed wavenumbers as fundamentals and lend support for 424 and 274 cm⁻¹ bands for POF₂Cl as the missing Raman bands. The F matrix elements obtained for these molecules were determined in such a way that F matrix elements common to POF₃, POF₂Cl, POFCl₂, and POCl₃ had nearly the same values and those common to PSF₃, PSF₂Br, PSFBr₂, and PSBr₃ also had nearly the same values. Finally, the values of the thermodynamic properties for these substances were computed for the ideal gaseous state using the rigid rotator harmonic oscillator approximation at 1 atm from 200 to 1000 K.