Spectrum and vibrational predissociation of the HF dimmer. I. Bound and quasibound states

摘要

We present full six-dimensional calculations of the bound states of the HF dimmer for total angular momentum J = 0,1 and of the quasibound states for J = 0 that correspond with vibrational excitation of one of the HF monomers, either the donor or the acceptor in the hydrogen bond. Transition frequencies and rotational constants were calculated for all four molecular symmetry blocks. A contracted discrete variable representation basis was used for the dimmer and monomer stretch coordinates, R, r_A, r_B; the generation of the monomer basis in the dimmer potential leads to significantly better convergence of the energies. We employed two different potential energy surfaces; the SQSBDE potential of Quack and Suhm and the SO-3 potential of Klopper, Quack, and Suhm. The frequencies calculated with the SO-3 potential agree very well with experimental data and are significantly better than those from the SQSBDE potential.