Variational quantum mechanical and active database approaches to the rotational-vibrational spectroscopy of ketene, H2CCO

A variational quantum mechanical protocol is presented for the computation of rovibrational energy levels of semirigid molecules using discrete variable representation of the Eckart-Watson Hamiltonian, a complete, exact inclusion of the potential energy surface, and selection of a vibrational subspace. Molecular symmetry is exploited via a symmetry-adapted Lanczos algorithm. Besides symmetry labels, zeroth-order rigid-rotor and harmonic-oscillator quantum numbers are employed to characterize the computed rovibrational states. Using the computational molecular spectroscopy algorithm presented, a large number of rovibrational states, up to J = 50, of the ground electronic state of the parent isotopologue of ketene, (H2C)-C-12=C-12=O-16, were computed and characterized. Based on 12 references, altogether 3982 measured and assigned rovibrational transitions of (H2C)-C-12=C-12=O-16 have been collected, from which 3194 were validated. These transitions form two spectroscopic networks (SN). The ortho and the para SNs contain 2489 and 705 validated transitions and 1251 and 471 validated energy levels, respectively. The computed energy levels are compared with energy levels obtained, up to J = 41, via an inversion protocol based on this collection of validated measured rovibrational transitions. The accurate inverted energy levels allow new assignments to be proposed. Some regularities and irregularities in the rovibrational spectrum of ketene are elucidated. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3625404]