The Infrared Spectrum of Chlorophosphaethyne, ClCP

Article abstract of DOI:10.1006/jmsp.1993.1241

C-Chlorophosphaethyne (ClC<*>P) has been generated by the pyrolysis of Cl3CPCl2 over granulated zinc at 550 deg C and the high-resolution spectrum in the region 4000-100 cm^-1 has been recorded, analyzed, and assigned.Altogether, more than 6500 transitions have been assigned.The observed bands include all three fundamentals as well as number of overtone, combination, and difference bands.For all the bands both the 35Cl and 37Cl isotopomers were observed, and for the ν₃ band the 35Cl13C isotopomer was observed in natural abundance.The ground state rotation constants B₀ and distorsion constants D₀ were found to be 0.10074626(10) and 1.2544(10)E-8 cm^-1 and 0.0981080(14) and 1.1950(16)E-8 cm^-1 for the 35Cl and 37Cl isotopomers, respectively, and 0.10073766(72) and 1.158(11)E-8 cm^-1 for the 13C species.After accounting for Fermi resonance effects the vibration-rotation parameters, α_i, for all three fundamentals have been estimated and used to calculate the equilibrium B values; B_e = 0.10094715(89) and 0.09830590(100) for the 35Cl and 37Cl isotopomers, respectively.The equilibrium geometry is calculated to be r_C<*>P=155.26(61) and r_C-Cl=163.41(62) pm.The available fundamental frequencies for all three isotopomers have been used to calculate the harmonic force constants: f_R(C-Cl)- 4.621; f_r(C<*>P)=9.033; f_Rr=0.499 aJ Angstroem^-2; and f_α=0.348 aJ.