Inversion of experimental data and ab initio studies of a pseudo-atom–diatom model for the vibrational dynamics of HCN–HF

Abstract

Spectroscopic data was inverted to generate simplified atom–diatom intermolecular potentials for the hydrogen bonded dimer HCN–HF. Both the HF ν1=0 and ν1=1 adiabatic surfaces of this complex involving the hydrogen bond stretch (ν4) and the high frequency HF bend (ν6) degrees of freedom were considered. Adiabatic separation of angular and radial degrees of freedom allowed a modified vibrational Rydberg–Klein–Rees (RKR) inversion to give effective radial potentials for each bending state. The final potential at a sequence of intermolecular separations was obtained by requiring agreement between the eigenvalues of the angular Hamiltonian and the effective radial potentials which were obtained from the RKR inversion. Potentials obtained from the inversion procedure were tested by a variational calculation with a basis set that consisted of products of preoptimized radial and angular eigenfunctions. Transition frequencies included in the inversion procedure were reproduced to better than 1 cm−1, respective rotational constants were predicted within 0.15% of the experimental value and predicted intensities were in qualitative agreement with experimental results. Ab initio potentials were also calculated using second order Mo/ller–Plesset perturbation theory to treat electron correlation effects and with a triple-zeta-valence basis set plus two sets of polarization functions. The energies were computed at geometries where the potential had been determined by the inversion procedure. A total of 264 geometries were considered. A correction for basis set superposition errors led to good agreement between ab initio and experimental values of the well depth. We calculated the bound states of the ab initio surfaces assuming the adiabatic separation of the ν1 mode from the ν4 and the ν6 modes. The transition frequencies calculated from the ab initio surface differed from the experimental energies by less than 20 cm−1 even for highly excited overtones. Both the potentials obtained from the inversion procedure and from the ab initio calculations were modified to predict the spectrum of HCN–DF.