Treating linear molecules in calculations of rotation-vibration spectra

Abstract

In this article, a numerical implementation of the exact kinetic energy operator (KEO) for triatomic molecules (symmetric of XY2-type and asymmetric of YXZ-type) is presented. The implementation is based on the valence coordinates with the bisecting (XY2-type molecules) and bond-vector (YXZ) embeddings and includes the treatment of the singularity at linear geometry. The KEO is represented in a sum-of-product form. The singularity caused by the undetermined angle at the linear configuration is resolved with the help of the associated Legendre and Laguerre polynomials used as parameterized bending basis functions in the finite basis set representation. The exact KEO implementation is combined with the variational solver theoretical rovibrational energies, equipped with a general automatic symmetry-adaptation procedure and efficient basis step contraction schemes, providing a powerful computational solver of triatomic molecules for accurate computations of highly excited ro-vibrational spectra. The advantages of different basis set choices are discussed. Examples of specific applications for computing hot spectra of linear molecules are given.