The combined use of SCF-MO calculations and experimental data in the evaluation of quadratic force fields: MOCIC potential functions for fluoroform, methyl acetylene, and methyl cyanide

Abstract

A semiempirical method combining SCF-MO calculations and limited vibrational data has been employed to evaluate the completely general quadratic potential fields of fluoroform, methyl acetylene, and acetonitrile. MOCIC (molecular orbital constraint using interaction coordinates) potential fields are presented for gas phase molecules of intermediate size. Here general harmonic force fields or excellent approximations utilizing extensive experimental data are available as standards. A statistical evaluation of the interaction potentials shows that there is some improvement in going from MNDO or ab initio SCF-MO force fields to the MOCIC functions which reliably reproduce the off-diagonal vibrational potential constants in most instances. The MOCIC primary compliants are excellent approximations of their vibrational counterparts, as expected. Comparison of the calculated isotopic frequencies, Coriolis coupling constants, and centrifugal distortion constants for the SCF-MO, MOCIC, and vibrational spectroscopic potential fields with the corresponding experimental values also shows MOCICs reliability for molecules with many interaction potentials. There is substantial improvement in the calculated isotopic frequency shifts and centrifugal distortion constants in going from SCF-MO to MOCIC functions.