A theoretical anharmonic study of the infrared absorption spectra of FHF−, FDF−, OHF−, and ODF− anions

Abstract

Anharmonic vibrational frequencies, equilibrium bond lengths, rotational constants, and vibrational absorption spectra have been calculated for the triatomic anions, FHF(-) and OHF(-), and the heavier isotopomers FDF(-) and ODF(-). The triatomic anions are assumed to maintain a collinear configuration throughout all calculations, so only the symmetric (nu(1)) and asymmetric (nu(3)) stretching modes are considered. The two-dimensional permanent dipole surfaces and potential energy surfaces are then constructed along bond coordinates, using high-level ab initio methods. Fundamental and combination bands are obtained from the vibrational eigenfunctions, resulting in anharmonic frequencies, which can be compared with the available theoretical and experimental data. The agreement is very good, especially for the pure symmetric modes, while the asymmetric ones show larger discrepancies, presumably due to the neglected coupling between stretching and bending modes. Strong inverse anharmonicity is found in the level spacing of the asymmetric modes, for both FHF(-) and OHF(-) anions. The calculated mixed modes (nnu(1)+mnu(3), n, m=0-3) also agree reasonably with the few available experimental data, supporting our model. Based on the vibrational eigenfunctions, isotope effects are also rationalized. Infrared absorption spectra are calculated from the dipole autocorrelation function for FHF(-) and FDF(-), and for OHF(-) and ODF(-). Peak locations and relative intensities are assigned in terms of the fundamental and mixed transitions.