Vibrational infrared intensities and polar tensors of 1,2-difluoroethylenes.
The polar tensors of cis and trans-1,2-difluoroethylenes have been determined with new normal modes based in a reassignment of nu(7) and nu(12) bands of the trans isomers and frequency values corrected for Fermi resonances and phase shifts. The signs of the dipole moment derivatives (and its directions, for B(u) symmetry species) were considered to be those of MP2/6-31G** estimates. Root mean square errors calculated for the new tensor element values from each pair of isotopomers (trans-1,2-C(2)H(2)F(2)/trans-1,2-C(2)D(2)F(2) and cis-1,2-C(2)H(2)F(2)/cis-1,2-C(2)D(2)F(2)) show that the new polar tensor sets fit the isotopic invariance criterion better than previously reported sets. The accuracy of polar tensor transference procedures was tested by calculating the infrared intensities of trans-1,2-C(2)H(2)F(2) through the new polar tensors of the cis isomer. The resulting estimates are very accurate and also support the new band assignment, though the A(6) intensity remains still somewhat underestimated.
Departamento de Química, Federal University of Paraná, Centro Politécnico, Av. Francisco H. dos Santos, s/n, Jardim das Américas, CP 19081, 81531-990 Curitiba, PR, Brazil. hpmf@quimica.ufpr.br
Harley P Martins
HP
Filho
D003627:Data Interpretation, Statistical; D005030:Ethylenes / Q000737:chemistry*; D013055:Spectrophotometry, Infrared
D005030:Ethylenes; C418472:1,2-fluoroethene