title: Complete nuclear motion Hamiltonian in the irreducible normal mode tensor operator formalism for the methane molecule.
abstract: A rovibrational model based on the normal-mode complete nuclear Hamiltonian is applied to methane using our recent potential energy surface [A. V. Nikitin, M. Rey, and Vl. G. Tyuterev, Chem. Phys. Lett. 501, 179 (2011)]. The kinetic energy operator and the potential energy function are expanded in power series to which a new truncation-reduction technique is applied. The vibration-rotation Hamiltonian is transformed systematically to a full symmetrized form using irreducible tensor operators. Each term of the Hamiltonian expansion can be thus cast in the tensor form whatever the order of the development. This allows to take full advantage of the symmetry properties for doubly and triply degenerate vibrations and vibration-rotation states. We apply this model to variational computations of energy levels for (12)CH(4), (13)CH(4), and (12)CD(4).
authors: Groupe de Spectrométrie Moléculaire et Atmosphérique, UMR CNRS 6089, BP 1039, F-51687, Reims Cedex 2, France. michael.rey@univ-reims.fr
authors: Michaël
authors: M
authors: Rey
authors: Andrei V
authors: AV
authors: Nikitin
authors: Vladimir G
authors: VG
authors: Tyuterev