Variational Calculations of Rovibrational Energy Levels and Transition Intensities for Tetratomic Molecules

Abstract

A description is given of an algorithm for computing rovibrational energy levels for tetratomic molecules. The expressions required for evaluating transition intensities are also given. The variational principle is used to determine the energy levels, and the kinetic energy operator is simple and evaluated exactly. The computational procedure is split up into the determination of one-dimensional radial basis functions, the computation of a contracted rotational−bending basis, followed by a final variational step coupling all degrees of freedom. An angular basis is proposed whereby the rotational−bending contraction takes place in three steps. Angular matrix elements of the potential are evaluated by expansion in terms of a suitable basis, and the angular integrals are given in a factorized form which simplifies their evaluation. The basis functions in the final variational step have the full permutation symmetries of the identical particles. Sample results are given for HCCH and BH3.