Interaction potentials and rovibrational spectroscopy of He(N)-OCS complexes.
We present a new vibrationally averaged He-OCS potential energy surface that is obtained from a combination of Møller-Plesset perturbation theory for the helium-molecule interaction and coupled cluster theory for the intramolecular vibrational potential. Employing this potential in quantum Monte Carlo calculations for He(N)-OCS complexes shows a blueshift of the OCS vibration for small N that is followed by a transition to a redshift for larger N. The size dependence of the vibrational shift is in good agreement with recent experimental measurements. We then make a comparative study of the effective rotational spectroscopic constants B(eff) and D(eff) calculated for small N values with this vibrationally averaged potential, with the corresponding values obtained from three previous He-OCS potentials. We find that the vibrationally averaged potential provides the most accurate description of the spectroscopic constants over the size range N=1-8 for which experimental data are available. We rationalize this improved description in terms of the detailed differences in the secondary minimum and saddle point regions of the underlying He-OCS interaction potential, in addition to the behavior at the lowest potential minimum. This analysis indicates that the spectroscopy of complexes with N>1 provides valuable information on the shape of the potential energy surface in regions that are not accessed by the N=1 He-OCS complex, but that are important for understanding the molecular spectroscopy in larger complexes and in droplets.
Paesani
F
F
Department of Chemistry and Pitzer Center for Theoretical Chemistry, University of California, Berkeley, California 94720, USA.
Whaley
K B
KB