Six-dimensional variational calculation of the bending energy levels of HF trimer and DF trimer

Abstract

The bending energy levels of HF and DF trimer were calculated variationally using a six-dimensional kinetic-energy operator derived by constraining the stretch degrees of freedom to their equilibrium values. A basis of direct products of spherical harmonics is used to represent the wave function. The symmetry adapted Lanczos method is used to calculate levels of all symmetries from one sequence of matrix-vector products. Two efficient ways of implementing the symmetry-adapted Lanczos method are presented. To determine the concerted hydrogen bond breaking tunneling splitting in HF and DF trimer one needs to use the D3h point group. By doing D3h calculations, we find that the splitting is negligible for the low-lying levels. If the tunneling is unfeasible, the appropriate group is C3h. Our calculation using the most accurate SO-3+HF3BG potential developed by Quack, Stohner, and Suhm indicates that two gas-phase overtone bending bands of HF trimer should be reassigned, and that the noble gas matrix spectra of the bending fundamental bands are significantly shifted from their gas-phase counterparts.