A chemometric analysis of ab initio vibrational frequencies and infrared intensities of methyl fluoride

Factorial design and principal component analyses are applied to CH3F infrared frequencies and intensities calculated from ab initio wave functions. In the factorial analysis, the quantitative effects of changing from a 6-31G to a 6-311G basis, of including polarization and diffuse orbitals, and of correcting for electron correlation using the second-order Moller-Plesset procedure are determined for all frequencies and intensities. The most significant main effect observed for the frequencies corresponds to the shift from Hartree-Fock to MP2 calculations, which tends to lower all frequency values by approximately 100 cm(-1). For the intensities, the main effects are larger for the CF stretching and the CH3 asymmetric stretching modes. Interaction effects between two or more of the four factors are found to be of minor importance, except for the interaction between correlation and polarization. The principal component analysis indicates that wave functions with polarization and diffuse orbitals at the second-order Moller-Plesset level provide the best estimates for the harmonic frequencies, but not for the intensities. For the frequencies, the first principal component distinguishes between MP2 and Hartree-Fock calculations, while the second component separates the wave functions with polarization orbitals from those without these orbitals. For the intensities, the separation is similar but less well defined. This analysis also shows that wave function optimization to calculate accurate intensities is more difficult than an optimization for frequencies. (C) 1996 by John Wiley & Sons, Inc.