THE PREDICTION OF SPECTROSCOPIC PROPERTIES FROM QUARTIC CORRELATED FORCE-FIELDS - HCCF, HFCO, SIH3+

Knowledge of a force field expanded through quartic displacements, together with a dipole field expanded through cubic displacements, yields all the harmonic and anharmonic molecular properties of interest to infrared spectroscopists. Such force fields may also explain much of the mechanism behind intramolecular vibrational energy redistribution. The ab initio quantum chemist can now calculate these fields, either at the self-consistent field level or with the inclusion of electron correlation effects. For accurate predictions, it is important to include electron correlations effects for at least the quadratic part of the force fields. Here we report studies using the second-order Møller-Plesset method for the full quartic fields. We examine the effects of using large basis sets. The quadratic force constants are calculated analytically; cubic and quartic constants are calculated using central differences of second derivatives in reduced normal coordinates. Three molecules are studied. HCCF, for which a large quantity of experimental data has been recently analyzed by Holland, Newnham, and Mills. The calculations are sufficiently accurate that errors in the experimental assignments became apparent. HFCO, where the theoretical anharmonic constants are helpful in understanding the highly excited vibrational states probed by Moore and co-workers. SiH3 +, whose high resolution absorption spectra has just recently been detected by Davies and co-workers. The conclusions are that this straightforward way of calculating spectroscopic properties is an extremely valuable tool for the understanding of spectroscopy. © 1990 American Institute of Physics.