title: Computational study of the rovibrational spectrum of CO₂-CS₂.
abstract: A new intermolecular potential energy surface, rovibrational transition frequencies, and line strengths are computed for CO2-CS2. The potential is made by fitting energies obtained from explicitly correlated coupled-cluster calculations using an interpolating moving least squares method. The rovibrational Schrödinger equation is solved with a symmetry-adapted Lanczos algorithm and an uncoupled product basis set. All four intermolecular coordinates are included in the calculation. In agreement with previous experiments, the global minimum of the potential energy surface (PES) is cross shaped. The PES also has slipped-parallel minima. Rovibrational wavefunctions are localized in the cross minima and the slipped-parallel minima. Vibrational parent analysis was used to assign vibrational labels to rovibrational states. Tunneling occurs between the two cross minima. Because more than one symmetry operation interconverts the two wells, the symmetry (-oo) of the upper component of the tunneling doublet is different from the symmetry (-ee) of the tunneling coordinate. This unusual situation is due to the multidimensional nature of the double well tunneling. For the cross ground vibrational state, calculated rotational constants differ from their experimental counterparts by less than 0.0001 cm(-1). Most rovibrational states were found to be incompatible with the standard effective rotational Hamiltonian often used to fit spectra. This appears to be due to coupling between internal and overall rotation of the dimer. A simple 2D model accounting for internal rotation was used for two cross-shaped fundamentals to obtain good fits.
authors.affiliation: Department of Physics, Engineering Physics, and Astronomy, Queen's University, Kingston, Ontario K7L 3N6, Canada.
authors.forename: James
authors.initials: J
authors.lastname: Brown
authors.affiliation: Chemistry Department, Queen's University, Kingston, Ontario K7L 3N6, Canada.
authors.forename: Xiao-Gang
authors.initials: XG
authors.lastname: Wang
authors.affiliation: Chemistry Department, Queen's University, Kingston, Ontario K7L 3N6, Canada.
authors.forename: Tucker
authors.initials: T
authors.lastname: Carrington
authors.affiliation: Department of Chemistry, Missouri University of Science and Technology, Rolla, Missouri 65409-0010, USA.
authors.forename: G S
authors.initials: GS
authors.lastname: Grubbs
authors.affiliation: Department of Chemistry, Missouri University of Science and Technology, Rolla, Missouri 65409-0010, USA.
authors.forename: Richard
authors.initials: R
authors.lastname: Dawes