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.



Research Center/Lab(s)

Center for High Performance Computing Research

Keywords and Phrases

Coupled-cluster calculations; Ground vibrational state; Intermolecular potential energy surfaces; Interpolating moving least-squares methods; Multidimensional nature; Rotational hamiltonians; Rovibrational spectrum; Rovibrational transitions; Potential energy surfaces; Quantum chemistry Engineering main heading: Carbon dioxide

International Standard Serial Number (ISSN)


Document Type

Article - Journal

Document Version

Final Version

File Type





© 2014 American Institute of Physics (AIP), All rights reserved.

Publication Date

01 Mar 2014